Supporting Information

Facile synthesis of β-germyl-α-amino amides via Pd(II)-

catalyzed primary and secondary C(sp3)–H bonds

germylation

Zheng-Xin Zhou,† Wei-Hao Rao,‡ Ming-Hua Zeng,† and Yue-Jin Liu*,†

†Hubei Collaborative Innovation Center for Advanced Chemical Materials, Ministry of Education Key Laboratory for the Synthesis and Application of Organic Functional Molecules, and College of Chemistry and Chemical Engineering, Hubei University, Wuhan 430062, China‡ College of Chemistry and Chemical Engineering, Xinyang Normal University, Xinyang, 464000, China§

Table of Contents:

1. General information S2

2. Experimental Section S3

2.1 Optimization for C(sp3)-H Germylation S3

2.2 General Procedure for C(sp3)-H Germylation S3

2.3 Scale-up Reaction for C(sp3)-H Germylation S4

2.4 Removal of directing group S15

2.5 Mechanistic Investigation S15

3. References S16

4. Spectra S17

S1

Electronic Supplementary Material (ESI) for ChemComm.This journal is © The Royal Society of Chemistry 2018

1. General Information

Toluene was dried by Sodium, distilled under reduced pressure and stored under

nitrogen. Pd(OAc)2 (Stream), Ag2CO3 (Adamas), BINA-PO2H (Adamas) were

purchased from above mentioned company and used without additional purification.

Other chemical reagents were commercially available and directly used without any

further purification. NMR spectra were recorded on a Bruke Avance operating for 1H

NMR at 400 MHz, 13C NMR at 100 MHz, and 19F NMR at 376 MHz, using TMS as

internal standard. The peaks were internally referenced to TMS (0.00 ppm) or residual

undeuterated solvent signal (7.26 ppm for 1H NMR and 77.16 ppm for 13C NMR).

The following abbreviations (or combinations thereof) were used to explain

multiplicities: s = singlet, d = doublet, t = triplet, m = multiplet, b = broad. High

resolution mass spectroscopy (HRMS) analyses were performed at a Thermo

Scientific Exactive Plus. Inc mass instrument (ESI).

.

S2

2. Experimental Section

2.1 Optimization for C(sp3)-H Germylation

a The reactions were carried out 1a (0.10 mmol), 2 (0.50 mmol), Pd(OAc)2 (0.010 mmol), ligand(0.03 mmol), Ag2CO3 (0.20 mmol), NaHCO3 (0.20 mmol), LiOAc (0.05 mmol), toluene (1.0 mL),air, 125 C, 12 h. Yield of 1H NMR. b Isolated yield.

Pd(OAc)2 (10 mol%)

Ag2CO3, NaHCO3LiOAc, toluene,125 C

ligand (30 mol%)[GeMe3]2

1a 3a2

Entrya Yield of 3a

4

5

6

7

8 BINA-PO2H

55%

58%

45%

71%b

38%

Ligand

N-Boc-Val-OH

N-Boc-lle-OH

N-Boc-Ala-OH

BINA-PO2H

1

2

3

37%

42%

46%

AdCOOH

PivOH

MesCO2H

3.0 eq.

[GeMe3]2

5.0 eq.

5.0 eq.

5.0 eq.

5.0 eq.

5.0 eq.

5.0 eq.

5.0 eq.

NHQ

O

NPhthNHQ

O

NPhthH Me3Ge

9 BINA-PO2H 20%1.5 eq.

+

2.2 General Procedure for C(sp3)-H Germylation

Pd(OAc)2 10 mol%

Ag2CO3, NaHCO3LiOAc, toluene, 125 oC

BINA-PO2H 30 mol%

[Me3Ge]2 2

CONHQ

R,R

H

CONHQ

R,R

GeMe3

To an oven-dried 50 mL screw-capped vial was added substrate amides (0.15 mmol),

hexamethylgermane (0.75 mmol), Pd(OAc)2 (3.5 mg, 0.015 mmol), BINA-PO2H

(15.2 mg, 0.045 mmol), Ag2CO3 (82.8 mg, 0.3 mmol), NaHCO3 (25.2 mg, 0.3 mmol),

LiOAc (4.7 mg, 0.075 mmol), toluene (1.0 mL). The mixture was stirred for 10 h at

125 °C under air followed by cooling. The resulting mixture was filtered through a

S3

celite pad and concentrated in vacuo. The residue was purified by preparative TLC

using hexane/EtOAc as the eluent to afford the product.

2.3 Scale-up Reaction for C(sp3)-H Germylation

Pd(OAc)2 10 mol%

Ag2CO3, NaHCO3LiOAc, toluene, 125 oC

BINA-PO2H 30 mol%

[Me3Ge]2 2

PhthN CONHQ PhthN CONHQ

GeMe3H1a 3a

To an oven-dried 50 mL screw-capped vial was added substrate amides (1.0 mmol),

hexamethylgermane (5.0 mmol), Pd(OAc)2 (23 mg, 0.1 mmol), BINA-PO2H (0.3

mmol), Ag2CO3 (2.0 mmol), NaHCO3 (2.0 mmol), LiOAc (1.0 mmol), toluene (5.0

mL). The mixture was stirred for 24 h at 125 °C under air followed by cooling. The

resulting mixture was filtered through a celite pad and concentrated in vacuo. The

residue was purified by flash column chromatography using hexane/EtOAc as the

eluent to afford the product 3a in 65% yield.

NHO

N

N

O

O

GeMe3

(R)-2-(1,3-dioxoisoindolin-2-yl)-N-(quinolin-8-yl)-3-

(trimethylgermyl)propanamide 3a

1H NMR (400 MHz, CDCl3) δ = 10.47 (br, 1H), 8.75 (dd, J=4.4, 1.6, 1H), 8.72 (t,

J=4.4, 1H), 8.14 (dd, J=8.4, 1.6, 1H), 7.89 (dd, J=5.6, 3.1, 2H), 7.74 (dd, J=5.6, 3.1,

2H), 7.50 (d, J=4.4, 2H), 7.43 (dd, J=8.4, 4.4, 1H), 5.23 (dd, J=12.0, 5.6, 1H), 2.20

(dd, J=13.6, 12.0, 1H), 1.80 (dd, J=13.6, 5.6, 1H), 0.18 (s, 9H); 13C NMR (100 MHz,

CDCl3) δ = 168.37, 168.19, 148.51, 138.75, 136.41, 134.34, 134.20, 132.11, 128.03,

127.45, 123.71, 122.00, 121.74, 116.79, 53.25, 17.21, -1.80; HRMS (EI-TOF) calcd

for C23H23N3O3GeNa (M+Na)+: 486.0843, found: 486.0833.

S4

NHO

N

N

O

O

GeMe3

Ph

(2R,3S)-2-(1,3-dioxoisoindolin-2-yl)-3-phenyl-N-(quinolin-8-yl)-3-

(trimethylgermyl)propanamide 3b1H NMR (400 MHz, CDCl3) δ = 10.85 (s, 1H), 8.90 (dd, J=4.4, 1.6, 1H), 8.80 (dd,

J=5.6, 3.2, 1H), 8.14 (dd, J=8.4, 1.6, 1H), 7.71-7.68 (m, 2H), 7.59-7.53-7.50 (m, 2H),

7.53-7.50 (m, 2H), 7.45 (dd, J=8.4, 4.4, 1H), 7.14-7.08 (m, 4H), 6.97-6.93 (m, 1H),

5.64 (d, J=13.6, 1H), 4.00 (d, J=13.6, 1H), 0.13 (s, 9H); 13C NMR (100 MHz, CDCl3)

δ = 168.24, 167.14, 148.78, 140.29, 138.93, 136.28, 134.56, 134.06, 131.44, 128.43,

128.06, 127.38, 125.41, 123.45, 122.23, 121.77, 117.39, 59.42, 36.62, -2.19; HRMS

(EI-TOF) calcd for C29H27N3O3Ge Na (M+Na)+: 562.1162, found: 562.1147.

NHO

N

N

O

O

GeMe3

OMe

(2R,3S)-2-(1,3-dioxoisoindolin-2-yl)-3-(4-methoxyphenyl)-N-(quinolin-8-yl)-3-

(trimethylgermyl)propanamide 3c

dr~15:1 estimated by 1H NMR. 1H NMR (400 MHz, CDCl3)δ = 10.86 (br, 1H), 8.90

(dd, J=4.4, 1.6, 1H), 8.79 (dd, J=5.6, 3.2, 1H), 8.14 (dd, J=8.4, 1.6, 1H), 7.71 (dd,

J=5.6, 3.0, 2H), 7.58 (dd, J=5.6, 3.0, 2H), 7.52-7.50 (m, 2H), 7.45 (dd, J=8.4, 4.4, 1H),

5.57 (d, J=13.6, 1H), 3.93 (d, J=13.6, 1H), 3.66 (s, 3H), 0.12 (s, 9H); 13C NMR (100

MHz, CDCl3) δ = 168.26, 167.22, 157.33, 148.76, 138.93, 136.26, 134.58, 134.07,

132.19, 131.47, 128.06, 127.38, 123.47, 122.21, 121.75, 117.39, 113.89, 59.71, 55.18,

35.54, -2.21; HRMS (EI-TOF) calcd for C30H29N3O4GeNa (M+Na)+: 592.1268,

found: 592.1254.

S5

NHO

N

N

O

O

GeMe3

Et

(2R,3S)-2-(1,3-dioxoisoindolin-2-yl)-3-(4-ethylphenyl)-N-(quinolin-8-yl)-3-

(trimethylgermyl)propanamide 3d1H NMR (400 MHz, CDCl3) δ = 10.86 (br, 1H), 8.90 (dd, J=4.4, 1.6, 1H), 8.80 (dd,

J=5.6, 3.2, 1H), 8.14 (dd, J=8.4, 1.6, 1H), 7.70 (dd, J=5.6, 3.2, 2H), 7.57 (dd, J=5.6,

3.2, 2H), 7.53-7.51 (m, 2H), 7.45 (dd, J=8.4, 4.4, 1H), 6.99 (d, J=8.4, 2H), 6.93 (d,

J=8.0, 2H), 5.61 (d, J=13.6, 1H), 3.95 (d, J=13.6, 1H), 2.44 (d, J=7.6, 2H), 1.04 (t,

J=7.6, 3H), 0.13 (s, 9H); 13C NMR (100 MHz, CDCl3) δ = 168.30, 167.28, 148.77,

141.18, 138.95, 137.15, 136.26, 134.61, 133.98, 131.53, 128.06, 127.83, 127.38,

123.42, 122.20, 121.75, 117.40, 59.69, 36.15, 28.33, 15.44, -2.17; HRMS (EI-TOF)

calcd for C31H31N3O3Ge Na (M+Na)+: 590.1475, found: 590.1460.

NHO

N

N

O

O

GeMe3

Me

(2R,3S)-2-(1,3-dioxoisoindolin-2-yl)-N-(quinolin-8-yl)-3-(p-tolyl)-3-

(trimethylgermyl)propanamide 3e

dr ~ 12.5:1 estimated by 1H NMR. 1H NMR (400 MHz, CDCl3)δ = 10.86 (br, 1H),

8.90 (dd, J=4.4, 1.6, 1H), 8.79 (dd, J=5.6, 3.2, 1H), 8.14 (dd, J=8.4, 1.6, 1H), 7.70 (td,

J=5.6, 2.4, 2H), 7.58 (dd, J=5.6, 3.2, 2H), 7.53-7.50 (m, 2H), 7.45 (dd, J=8.4, 4.4, 1H),

6.98 (d, J=8.0, 2H), 6.92 (d, J=8.0, 2H), 5.61 (d, J=13.6, 1H), 3.96 (d, J=13.6, 1H),

2.15 (s, 3H), 0.12 (s, 9H); 13C NMR (100 MHz, CDCl3) δ = 168.25, 167.24, 148.77,

138.95, 136.93, 136.26, 134.74, 134.60, 134.01, 131.52, 129.14, 128.06, 127.38,

123.47, 122.20, 121.75, 117.39, 59.61, 36.08, 21.02, -2.21; HRMS (EI-TOF) calcd

for C30H29N3O3Ge Na (M+Na)+: 576.1318, found: 576.1302.

S6

NHO

N

N

O

O

GeMe3

Br

(2R,3S)-3-(4-bromophenyl)-2-(1,3-dioxoisoindolin-2-yl)-N-(quinolin-8-yl)-3-

(trimethylgermyl)propanamide 3f

dr ~ 4:1 estimated by 1H NMR. 1H NMR of main product (400 MHz, CDCl3) δ =

10.78 (br, 1H), 8.88 (dd, J=4.4, 1.6, 1H), 8.79-8.76 (m, 1H), 8.14 (dd, J=8.4, 1.6, 1H),

7.73 (dd, J=5.6, 3.2, 2H), 7.62 (dd, J=5.6, 3.2, 2H), 7.52 (d, J=4.0, 2H), 7.45 (dd,

J=8.4, 4.4, 1H), 7.27-7.25 (m, 2H), 6.98 (d, J=8.4, 2H), 5.58 (d, J=13.6, 1H), 4.00 (d,

J=13.6, 1H), 0.13 (s, 9H); 13C NMR (100 MHz, CDCl3) δ = 168.19, 166.76, 148.79,

139.63, 138.89, 136.31, 134.44, 134.27, 134.07, 131.59, 131.36, 128.44, 128.07,

127.39, 123.63, 123.47, 122.33, 121.81, 119.03, 117.39, 58.95, 36.12, -2.19, -2.22;

HRMS (EI-TOF) calcd for C29H26BrN3O3Ge Na (M+Na)+: 640.0267, found:

640.0248.

NHO

N

N

O

O

GeMe3

F

(2R,3S)-2-(1,3-dioxoisoindolin-2-yl)-3-(4-fluorophenyl)-N-(quinolin-8-yl)-3-

(trimethylgermyl)propanamide 3g1H NMR (400 MHz, CDCl3) δ 10.82 (s, 1H), 8.88 (dd, J = 4.0, 1.6 Hz, 1H), 8.79 (dd,

J = 5.2, 3.6 Hz, 1H), 8.14 (dd, J = 8.4, 1.6 Hz, 1H), 7.72 (dd, J = 5.6, 3.2 Hz, 2H),

7.61 (dd, J = 5.6, 3.2 Hz, 2H), 7.45 (dd, J = 8.4, 4.2 Hz, 1H), 7.05 (dd, J = 8.8, 5.2 Hz,

2H), 6.83 (t, J = 8.8 Hz, 2H), 5.58 (d, J = 13.6 Hz, 1H), 3.98 (d, J = 13.6 Hz, 1H),

0.14 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 168.20, 166.90, 160.85, 148.78, 138.91,

136.30, 136.12(d, J = 3.1 Hz),134.49, 134.22, 131.36, 128.94, 128.06, 127.39, 123.54,

122.04 (d, J = 50.1 Hz), 117.38, 115.33(d, J = 21.1 Hz), 59.39, 35.76, -2.21; 19F NMR

(376 MHz, CDCl3) δ -117.79; HRMS (EI-TOF) calcd for C29H26FN3O3GeNa

(M+Na)+: 580.1068, found: 580.1057.

S7

NHO

N

N

O

O

GeMe3OMe

(2R,3S)-2-(1,3-dioxoisoindolin-2-yl)-3-(3-methoxyphenyl)-N-(quinolin-8-yl)-3-

(trimethylgermyl)propanamide 3h

D.r. = 15:1 estimated by 1H NMR. 1H NMR (400 MHz, CDCl3) δ = 10.86 (br, 1H),

8.89 (dd, J=4.4, 1.6, 1H), 8.80 (dd, J=5.6, 3.2, 1H), 8.14 (dd, J=8.4, 1.6, 1H), 7.71 (dd,

J=5.6, 3.2, 2H), 7.58 (dd, J=5.6, 3.2, 2H), 7.53-7.51 (m, 2H), 7.45 (dd, J=8.4, 4.4, 1H),

5.73 (d, J=13.2, 0H), 5.63 (d, J=13.6, 1H), 3.98 (d, J=13.6, 1H), 3.71 (s, 3H), 0.15 (s,

9H); 13C NMR (100 MHz, CDCl3) δ = 168.23, 167.08, 159.56, 148.77, 141.90,

138.93, 136.27, 134.56, 134.08, 131.48, 129.38, 128.06, 127.37, 123.48, 122.23,

121.76, 117.40, 111.65, 59.37, 55.24, 36.75, -2.13; HRMS (EI-TOF) calcd for

C30H29N3O4Ge Na (M+Na)+: 592.1268, found: 592.1254.

NHO

N

N

O

O

GeMe3F

(2R,3S)-2-(1,3-dioxoisoindolin-2-yl)-3-(3-fluorophenyl)-N-(quinolin-8-yl)-3-

(trimethylgermyl)propanamide 3i

dr~14:1 estimated by 1H NMR. 1H NMR (400 MHz, CDCl3) δ = 10.80 (br, 1H), 8.88

(dd, J=4.4, 1.6, 1H), 8.78 (dd, J=5.2, 4.0, 1H), 8.14 (dd, J=8.4, 1.6, 1H), 7.73 (dd,

J=5.6, 3.1, 2H), 7.60 (dd, J=5.6, 3.2, 2H), 7.53-7.51 (m, 2H), 7.44 (dd, J=8.4, 4.2, 1H),

7.10 (td, J=8.0, 6.4, 1H), 6.88 (d, J=8.0, 1H), 6.82 (dt, J=10.0, 2.0, 1H), 6.67 (td,

J=8.4, 2.0, 1H), 5.60 (d, J=13.5, 1H), 4.03 (d, J=13.6, 1H), 0.15 (s, 9H); 13C NMR

(100 MHz, CDCl3) δ = 168.13, 166.75, 162.81 (d, J=244.2), 148.78, 143.27 (d, J=7.3),

138.87, 136.29, 134.43, 134.19, 131.36, 129.89, 128.04 (s, 3H), 127.36, 123.56,

122.31, 121.79, 117.36, 112.45 (d, J=21.1), 59.02, 36.59, -2.17; 19F NMR (376 MHz,

CDCl3) δ -112.97; HRMS (EI-TOF) calcd for C29H26N3O3Ge Na (M+Na)+: 580.1068,

found: 580.1051.

S8

NHO

N

N

O

O

GeMe3S

(2R,3R)-2-(1,3-dioxoisoindolin-2-yl)-N-(quinolin-8-yl)-3-(thiophen-2-yl)-3-

(trimethylgermyl)propanamide 3j

dr ~ 4:1 estimated by 1H NMR. 1H NMR of the main product (400 MHz, CDCl3) δ =

10.84 (s, 1H), 8.90 (dd, J=4.4, 1.6, 1H), 8.78 (t, J=4.4, 1H), 8.14 (dd, J=8.4, 1.6, 1H),

8.07 (dd, J=8.4, 1.6, 0H), 7.77-7.74 (m, 2H), 7.62 (dd, J=5.6, 3.2, 2H), 7.52 (d, J=4.4,

2H), 7.45 (dd, J=8.4, 4.4, 1H), 6.88 (d, J=5.2, 1H), 6.76-6.72 (m, 2H), 5.48 (d, J=13.2,

1H), 4.34 (d, J=13.2, 1H), 0.20 (s, 9H); 13C NMR (100 MHz, CDCl3) δ = 168.20,

166.67, 148.81, 143.39, 138.93, 136.28, 134.50, 134.15, 131.52, 128.06, 127.36,

126.82, 124.13, 123.92, 123.56, 122.34, 122.31, 121.78, 117.45, 60.76, 31.29, -2.20;

HRMS (EI-TOF) calcd for C27H25SN3O3GeNa (M+Na)+: 568.0726, found: 568.0707.

NAc

GeMe3O

HN

N

(2R,3S)-1-acetyl-N-(quinolin-8-yl)-3-(trimethylgermyl)pyrrolidine-2-

carboxamide 3k1H NMR (400 MHz, CDCl3) δ 9.93 (br, 1H), 8.55 (dd, J = 4.0, 1.6 Hz, 1H), 8.31 (d, J

= 8.4 Hz, 1H), 8.01 (dd, J = 8.0, 1.6 Hz, 1H), 7.86 (d, J = 8.0 Hz, 1H), 7.78 (dd, J =

12.4, 7.6 Hz, 2H), 7.59-7.37 (m, 5H), 7.29 (dd, J = 8.0, 4.0 Hz, 1H), 4.64 (t, J = 7.6

Hz, 1H), 1.82 (dd, J = 14.8, 7.2 Hz, 1H), 1.52 (dd, J = 14.8, 8.4 Hz, 1H), -0.06 (s, 9H);

13C NMR (100 MHz, CDCl3) δ 173.29, 148.13, 138.54, 137.63, 136.16, 134.77,

134.40, 131.69, 129.19, 128.14, 127.89, 127.41, 126.61, 125.81, 125.77, 123.60,

121.50, 121.34, 116.17, 46.81, 20.75, -1.03; HRMS (EI-TOF) calcd for

C19H25N3O2Ge Na (M+Na)+: 424.1056, found: 424.1037.

S9

ON

HN

GeMe3

2-phenyl-N-(quinolin-8-yl)-3-(trimethylgermyl)propanamide 5a

1H NMR (400 MHz, CDCl3) δ 9.93 (br, 1H),8.76- 8.74 (m, 2H), 8.10 (dd, J = 8.0, 1.6

Hz, 1H), 7.51-7.24 (m, 8H), 3.85 (dd, J = 9.2, 7.2 Hz, 1H), 1.75 (dd, J = 13.6, 6.8 Hz,

1H), 1.51 (dd, J = 13.6, 9.2 Hz, 1H), 0.05 (s, 9H); 13C NMR (100 MHz, CDCl3) δ

173.18, 148.26, 141.57, 138.64, 136.36, 134.76, 128.97, 128.09, 128.01, 127.51,

127.45, 121.62, 121.46, 116.40, 51.81, 21.39, -1.73; HRMS (EI-TOF) calcd for

C21H24N2OGeNa (M+Na)+: 417.0998, found: 417.0980.

ON

HN

GeMe3

Me

N-(quinolin-8-yl)-2-(o-tolyl)-3-(trimethylgermyl)propanamide 5b1H NMR (400 MHz, CDCl3) δ 9.87 (br, 1H), 8.74 (d, J = 7.4 Hz, 1H), 8.68 (d, J = 2.8

Hz, 1H), 8.09 (d, J = 7.2 Hz, 1H), 7.55-7.43 (m, 3H), 7.37 (dd, J = 8.0, 4.0 Hz, 1H),

7.25-7.17 (m, 3H), 4.11 (dd, J = 8.4, 7.6 Hz, 1H), 2.52 (s, 3H), 1.79 (dd, J = 13.6, 7.2

Hz, 1H), 1.50 (dd, J = 13.6, 9.2 Hz, 1H), 0.07 (s, 9H); 13C NMR (100 MHz, CDCl3) δ

173.32, 148.24, 139.57, 138.62, 136.31, 135.91, 134.81, 130.95, 127.98, 127.54,

127.50, 127.24, 126.80, 121.58, 121.38, 116.31, 47.30, 20.73, 20.17, -1.59; HRMS

(EI-TOF) calcd for C22H26N2OGe Na (M+Na)+: 431.1155, found: 431.1139.

ON

HN

GeMe3

Cl

2-(2-chlorophenyl)-N-(quinolin-8-yl)-3-(trimethylgermyl)propanamide 5c

S10

1H NMR (400 MHz, CDCl3) δ 9.85 (br, 1H), 8.83-8.79 (m, 2H), 8.16 (dd, J = 8.0, 1.2

Hz, 1H), 7.56-7.44 (m, 3H), 2.58-2.51 (m, 1H), 1.87-1.78 (m, 1H), 1.60-1.53 (m, 1H),

1.40-1.25 (m, 8H), 1.13 (dd, J = 14.8, 8.8 Hz, 1H), 0.91-0.82 (m, 4H), 0.03 (s, 9H);

13C NMR (100 MHz, CDCl3) δ 175.71, 148.30, 138.63, 136.45, 134.75, 128.09,

127.63, 121.67, 121.36, 116.59, 45.31, 36.74, 31.85, 29.49, 27.69, 22.74, 21.11, 14.19,

-0.94; HRMS (EI-TOF) calcd for C21H23ClN2OGeNa (M+Na)+: 451.0608, found:

451.0588.

ON

HN

GeMe3

F

2-(2-fluorophenyl)-N-(quinolin-8-yl)-3-(trimethylgermyl)propanamide 5d1H NMR (400 MHz, CDCl3) δ10.04 (br, 1H), 8.78-8.74 (m, 2H), 8.11 (d, J = 8.0 Hz,

1H), 7.58 (t, J = 6.8 Hz, 1H), 7.52-7.45 (m, 2H), 7.41 (dd, J = 8.0, 4.0 Hz, 1H), 7.24-

7.21 (m, 1H), 7.16 (t, J = 7.2 Hz, 1H), 7.07 (t, J = 7.2 Hz, 1H), 4.27 (dd, J = 8.4, 7.6

Hz, 1H), 1.75 (dd, J = 13.6, 7.2 Hz, 1H), 1.51 (dd, J = 13.6, 8.8 Hz, 1H), 0.08 (s, 9H);

13C NMR (100 MHz, CDCl3) 172.28, 161.41 (d, J = 243.2 Hz), 148.38, 138.65,

136.32, 134.74, 129.36 (d, J = 3.8 Hz), 128.84 (d, J = 8.3 Hz), 128.52 (d, J = 14.6

Hz),128.01, 127.46, 124.74 (d, J = 3.5 Hz), 121.63 (d, J = 8.3 Hz), 116.52, 115.73,

115.50, 43.03 (d, J = 2.6 Hz), 20.17, -1.81; 19F NMR (376 MHz, CDCl3) δ -118.12;

HRMS (EI-TOF) calcd for C21H23FN2OGe Na (M+Na)+: 435.0904, found: 435.0888.

ON

HN

GeMe3Cl

2-(3-chlorophenyl)-N-(quinolin-8-yl)-3-(trimethylgermyl)propanamide 5e1H NMR (400 MHz, CDCl3) δ 9.96 (br, 1H), 8.77 (dd, J = 4.0, 1.6 Hz, 1H), 8.73 (dd,

J = 7.2, 1.6 Hz, 1H), 8.12 (dd, J = 8.4, 1.6 Hz, 1H), 7.52-7.38 (m, 5H), 7.30-7.23 (m,

2H), 3.83 (t, J = 8.0 Hz, 1H), 1.73 (dd, J = 13.6, 7.2 Hz, 1H), 1.46 (dd, J = 13.6, 8.8

Hz, 1H), 0.08 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 172.35, 148.32, 143.72, 138.54,

136.52, 134.74, 134.49, 130.15, 128.19, 128.04, 127.62, 127.52, 126.27, 121.72,

S11

116.62, 51.47, 21.52, -1.70; HRMS (EI-TOF) calcd for C21H23ClN2OGeNa (M+Na)+:

451.0608, found: 451.0588.

ON

HN

GeMe3F

2-(3-fluorophenyl)-N-(quinolin-8-yl)-3-(trimethylgermyl)propanamide 5f

1H NMR (400 MHz, CDCl3) δ = 9.95 (br, 1H), 8.77 (dd, J=4.4, 1.6, 1H), 8.73 (dd,

J=7.2, 1.6, 1H), 8.12 (dd, J=8.4, 1.6, 1H), 7.52-7.46 (m, 2H), 7.42 (dd, J=8.4, 4.4, 1H),

7.34-7.22 (m, 3H), 6.98-6.93 (m, 1H), 3.84 (dd, J=8.4, 7.6, 1H), 1.73 (dd, J=13.6, 7.2,

1H), 1.47 (dd, J=13.7, 8.8, 1H), 0.07 (s, 9H); 13C NMR (100 MHz, CDCl3) δ =

172.45, 164.44, 161.99, 148.36, 144.21, 144.14, 138.61, 136.43, 134.56, 130.41,

130.33, 128.03, 127.50, 123.81, 123.78, 121.71, 121.67, 116.50, 115.09, 114.87,

114.48, 114.27, 51.53, 51.51, 21.44, -1.72; 19F NMR (376 MHz, CDCl3) δ = -

112.59.；HRMS (EI-TOF) calcd for C21H23FN2OGeNa (M+Na)+: 435.0904, found:

435.0886.

ON

HN

GeMe3

F

2-(4-fluorophenyl)-N-(quinolin-8-yl)-3-(trimethylgermyl)propanamide 5g1H NMR (400 MHz, CDCl3) δ 9.93 (br, 1H), 8.76 (dd, J=4.4, 1.6, 1H), 8.73 (dd,

J=7.2, 1.6, 1H), 8.12 (dd, J=8.4, 1.6, 1H), 7.52-7.41 (m, 5H), 7.07-7.02 (m, 2H), 3.84

(dd, J=9.2, 6.8, 1H), 1.72 (dd, J=13.6, 6.8, 1H), 1.48 (dd, J=13.6, 9.2, 1H), 0.06 (s,

9H); 13C NMR (100 MHz, CDCl3) δ 173.03, 163.49, 161.05, 148.33, 138.61, 137.36,

137.32, 136.44, 134.60, 129.63, 129.55, 128.03, 127.50, 121.69, 121.63, 116.46,

115.86, 115.65, 51.00, 21.61, -1.71; 19F NMR (376 MHz, CDCl3) δ -115.46; HRMS

(EI-TOF) calcd for C21H23FN2OGeNa (M+Na)+: 435.0904, found: 435.0856.

S12

ON

HN

GeMe3

F3C

N-(quinolin-8-yl)-2-(4-(trifluoromethyl)phenyl)-3-(trimethylgermyl)propanamide

5h

1H NMR (400 MHz, CDCl3) δ10.47 (br, 1H), 8.75 (dd, J=4.4, 1.6, 1H), 8.72 (t, J=4.4,

1H), 8.14 (dd, J=8.4, 1.6, 1H), 7.89 (dd, J=5.2, 3.2, 2H), 7.74 (dd, J=5.2, 3.2, 2H),

7.50 (d, J=4.4, 2H), 7.43 (dd, J=8.4, 4.4, 1H), 5.23 (dd, J=12.0, 5.6, 1H), 2.20 (dd,

J=13.6, 12.0, 1H), 1.80 (dd, J=13.6, 5.6, 1H), 0.18 (s, 9H); 13C NMR (100 MHz,

CDCl3) δ172.22, 148.37, 142.66, 138.60, 136.45, 134.44, 131.54,131.22 (q, J=32.0),

129.39, 128.03, 127.48, 124.87 (q, J=3.8), 124.32 (q, J=3.8), 124.25 (q, J=270.8),

121.78 (d, J=1.8), 116.55, 51.63, 21.67, -1.73; 19F NMR (376 MHz, CDCl3) δ -62.52;

HRMS (EI-TOF) calcd for C22H23F3N2OGeNa (M+Na)+: 485.0872, found: 485.0856.

ON

HN

GeMe3

ClCl

2-(3,4-dichlorophenyl)-N-(quinolin-8-yl)-3-(trimethylgermyl)propanamide 5i1H NMR (400 MHz, CDCl3) δ9.95 (br, 1H), 8.79 (dd, J=4.4, 1.6, 1H), 8.71 (dd, J=6.8,

2.4, 1H), 8.14 (dd, J=8.0, 1.6, 1H), 7.62 (d, J=2.0, 1H), 7.53-7.34 (m, 5H), 3.80 (t,

J=8.0, 1H), 1.73 (dd, J=13.6, 8.0, 1H), 1.42 (dd, J=13.6, 8.4, 1H), 0.10 (s, 9H).; 13C

NMR (100 MHz, CDCl3) δ171.92, 148.44, 142.05, 138.57, 136.51, 134.38, 132.89,

131.45, 130.78, 129.97, 128.05, 127.50, 127.40, 121.86, 121.79, 116.60, 50.99, 21.60,

-1.64; HRMS (EI-TOF) calcd for C21H22Cl2N2OGeNa (M+Na)+: 485.2019, found:

485.0196.

S13

ON

HN

GeMe3

2-(naphthalen-2-yl)-N-(quinolin-8-yl)-3-(trimethylgermyl)propanamide 5j1H NMR (400 MHz, CDCl3) δ 10.95 (s, 1H), 8.86-8.84 (m, 2H), 8.15 (dd, J=8.4, 1.6,

1H), 7.58-7.53 (m, 2H), 7.45 (dd, J=8.4, 4.4, 1H), 7.15-7.05 (m, 3H), 6.91 (td, J=7.6,

0.8, 1H), 5.53 (d, J=9.2, 1H), 3.36 (d, J=9.2, 1H), 0.15 (s, 9H).; 13C NMR (100 MHz,

CDCl3) δ 173.04, 148.24, 139.15, 138.60, 136.32, 134.70, 133.76, 132.89, 128.75,

127.97, 127.95, 127.79, 127.47, 126.79, 126.26, 126.10, 125.88, 121.59, 121.49,

116.40, 51.93, 21.35, -1.62; HRMS (EI-TOF) calcd for C25H26N2OGeNa (M+Na)+:

476.1155, found: 476.1140.

ON

HN

GeMe3O

N-(quinolin-8-yl)-3-(trimethylgermyl)-2,3-dihydrobenzofuran-2-carboxamide 5k1H NMR (400 MHz, CDCl3) δ 10.95 (s, 1H), 8.86-8.84 (m, 2H), 8.15 (dd, J=8.4, 1.6,

1H), 7.58-7.53 (m, 2H), 7.45 (dd, J=8.4, 4.4, 1H), 7.15-7.05 (m, 3H), 6.91 (td, J=7.6,

0.8, 1H), 5.53 (d, J=9.2, 1H), 3.36 (d, J=9.2, 1H), 0.15 (s, 9H).; 13C NMR (100 MHz,

CDCl3) δ168.52, 157.73, 148.80, 138.95, 136.27, 133.90, 130.96, 128.15, 127.38,

126.95, 123.60, 122.33, 121.84, 121.73, 116.91, 110.05, 86.08, 36.63, -1.75; HRMS

(EI-TOF) calcd for C21H22N2O2Na (M+Na)+: 431.0791, found: 431.0773.

ON

HN

GeMe3O

N-(quinolin-8-yl)-3-(trimethylgermyl)tetrahydrofuran-2-carboxamide 5l1H NMR (400 MHz, CDCl3) δ 10.82 (br, 1H), 8.85 (dd, J=4.4, 1.6, 1H), 8.77 (dd,

J=6.4, 2.8, 1H), 8.14 (dd, J=8.4, 1.6, 1H), 7.55-7.49 (m, 2H), 7.44 (dd, J=8.4, 4.4, 1H),

S14

4.74-4.72 (m, 1H), 4.47-4.43 (m, 1H), 3.90-3.84 (m, 1H), 2.12-2.04 (m, 1H), 1.91-

1.82 (m, 2H), 0.23 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 171.65, 148.74, 139.04,

136.26, 134.17, 128.16, 127.42, 121.88, 121.70, 116.47, 82.21, 69.57, 32.62, 28.53, -

1.78; HRMS (EI-TOF) calcd for C17H22N2O2GeNa (M+Na)+: 383.0791, found:

383.0777.

2.4 Removal of Directing Group

BF3.Et2ONHQ

NPhth

O

3ab, 82%MeOH, 80 C

Me3Ge OMeNPhth

O

Me3Ge

3a

To an oven-dried 50 mL round-bottomed flask was added substrate 3a (0.1 mmol),

BF3·Et2O (1.0 mmol) in MeOH (1 mL). The flask was stirred for 12 h at 80 °C. The

crude product was purified by prepared column chromatography(Rf = 0.7, EtOAc/PE

= 1/5) to afford 3ab (31.0 mg, 85%). 1H NMR (400 MHz, CDCl3) δ 7.90 – 7.84 (m,

2H), 7.77 – 7.71 (m, 2H), 4.97 (dd, J = 11.1, 5.7 Hz, 1H), 3.72 (s, 3H), 1.80 (dd, J =

14.1, 11.1 Hz, 1H), 1.69 (dd, J = 14.1, 5.7 Hz, 1H), 0.10 (s, 9H). 13C NMR (101 MHz,

CDCl3) δ = 170.87, 167.42, 134.02, 131.71, 123.34, 52.65, 49.85, 16.98, -2.23.

HRMS (EI-TOF) calcd for C15H19GeNNaO4 (M+Na)+: 374.0424, found: 374.0415.

2.5 Mechanistic Investigation

Synthesis of Palladacycle Int-A

NH

Me

NPhth

O

Int-A1a

Pd(OAc)2 NPd

PhthNN

NCMe

N

O

DCM-MeCN

To an oven-dried 50 mL round-bottomed flask was added substrate 1a (1.0 mmol),

Pd(OAc)2 (1.0 mmol) in DCM (10 mL) and MeCN (5 mL). The flask was stirred for

12 h at 60 °C followed by cooling. The purified product was collected by filtration,

washed with MeCN, diethyl ether and dried under vacuum to afford Int-A (392 mg,

S15

80%) as yellow power.1 1H NMR (501 MHz, CDCl3) δ 8.93 (d, J = 7.5 Hz, 1H), 8.18

(s, 1H), 8.00 (d, J = 8.0 Hz, 1H), 7.83 (s, 2H), 7.68 (s, 2H), 7.40 (t, J = 8.0 Hz, 1H),

7.19 (d, J = 7.5 Hz, 1H), 7.15 (dd, J = 7.5, 4.5 Hz, 1H), 5.32 (t, J = 10.0 Hz, 1H), 2.40

(t, J = 9.0 Hz, 1H), 2.32 (s, 3H),1.95 (t, J = 8.0 Hz, 1H).

Stoichiometric Reaction of Int-A

Int-A

NHQNPhth

O

3a, 46%

(GeMe3)2 Me3Gestandard conditions

NPd

O

PhthNN

NCMe

To an oven-dried 50 mL screw-capped vial was added Int-A (0.1 mmol), 2 (0.5

mmol), BINA-PO2H (0.03 mmol), Ag2CO3 (0.2 mmol), NaHCO3 (0.2 mmol), LiOAc

(0.05 mmol), toluene (1.0 mL). The mixture was stirred for 10 h at 125 °C under air

followed by cooling. The resulting mixture was filtered through a celite pad and

concentrated in vacuo. The product 3a was obtained in 52% yield (determined by 1H

NMR).

Catalytic Reaction of Int-A

NHQMe

NPhth

O

1a

(GeMe3)2

standard conditions

cat. Int-A NHQNPhth

O

3a, 53%

Me3Ge

To an oven-dried 50 mL screw-capped vial was added 1a (0.1 mmol),2 (0.5 mmol),

Int-A (0.01 mmol), BINA-PO2H (0.03 mmol), Ag2CO3 (0.2 mmol), NaHCO3 (0.2

mmol), LiOAc (0.05 mmol), toluene (1.0 mL). The mixture was stirred for 10 h at 125

°C under air followed by cooling. The resulting mixture was filtered through a celite

pad and concentrated in vacuo. The product 3a was obtained in 28% yield

(determined by 1H NMR yield).

3. References:

S16

1. Liu, Y.-J.; Liu, Y.-H.; Zhang, Z.-Z.; Chen, K.; Shi, B.-F., Angew. Chem. Int. Ed.

2016, 55, 13859.

4. NMR Spectra

-2-1012345678910111213f1 (ppm)

8.92

1.00

1.03

1.00

1.03

2.00

1.99

1.96

0.99

1.00

1.00

0.96

0.17

7

1.77

81.

792

1.81

2

2.17

12.

200

2.20

42.

234

5.20

95.

222

5.23

95.

252

7.41

27.

444

7.73

37.

754

7.89

7

8.70

48.

727

8.74

9

10.4

75

1H NMR (400 MHz, CDCl3) δ = 10.47 (br, 1H), 8.75 (dd, J=4.4, 1.6, 1H), 8.72 (t, J=4.4, 1H), 8.14 (dd, J=8.4, 1.6, 1H), 7.89 (dd, J=5.6, 3.1, 2H), 7.74 (dd, J=5.6, 3.1, 2H), 7.50 (d, J=4.4, 2H), 7.43 (dd, J=8.4, 4.4, 1H), 5.23 (dd, J=12.0, 5.6, 1H), 2.20 (dd, J=13.6, 12.0, 1H), 1.80 (dd, J=13.6, 5.6, 1H), 0.18 (s, 9H).

S17

NHO

N

N

O

O

GeMe3

3a

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-1.7

96

17.2

06

53.2

48

116.7

9312

1.74

512

3.71

012

8.02

813

4.19

713

6.41

3

148.

510

168.

188

168.

371

13C NMR (101 MHz, CDCl3) δ = 168.37, 168.19, 148.51, 138.75, 136.41, 134.34, 134.20, 132.11, 128.03, 127.45, 123.71, 122.00, 121.74, 116.79, 53.25, 17.21, -1.80.

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.512.5f1 (ppm)

9.03

0.98

1.00

1.02

3.97

1.03

1.92

2.03

2.00

0.98

1.00

1.00

0.95

0.13

4

3.98

04.

014

5.62

25.

656

6.93

26.

956

7.12

47.

433

7.56

3

8.12

88.

148

8.78

68.

794

8.80

08.

809

8.88

98.

893

10.8

53

1H NMR (400 MHz, CDCl3) δ = 10.85 (s, 1H), 8.90 (dd, J=4.4, 1.6, 1H), 8.80 (dd, J=5.6, 3.2, 1H), 8.14 (dd, J=8.4, 1.6, 1H), 7.71-7.68 (m, 2H), 7.59-7.53-7.50 (m, 2H), 7.53-7.50 (m, 2H), 7.45 (dd, J=8.4, 4.4, 1H), 7.14-7.08 (m, 4H), 6.97-6.93 (m, 1H), 5.64 (d, J=13.6, 1H), 4.00 (d, J=13.6, 1H), 0.13 (s, 9H).

S18

NHO

N

N

O

O

GeMe3

3a

NHO

N

N

GeMe3

O

O3b

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-2.1

93

36.6

17

59.4

23

117.3

9012

1.76

512

2.23

412

3.45

512

5.41

412

7.38

512

8.06

212

8.43

313

1.43

713

4.06

3

136.

276

148.

776

167.

137

168.

235

13C NMR (101 MHz, CDCl3) δ = 168.24, 167.14, 148.78, 140.29, 138.93, 136.28, 134.56, 134.06, 131.44, 128.43, 128.06, 127.38, 125.41, 123.45, 122.23, 121.77, 117.39, 59.42, 36.62, -2.19.

-1.00.01.02.03.04.05.06.07.08.09.010.011.012.013.0f1 (ppm)

8.83

3.05

1.00

1.00

1.04

1.96

2.01

2.02

0.98

1.01

0.96

0.96

0.12

5

3.65

93.

916

3.95

0

5.55

75.

591

6.65

86.

688

7.02

47.

442

8.12

48.

145

8.78

28.

790

8.79

68.

804

8.90

2

10.8

58

d.r. = 15:1 determined by 1H NMR. 1H NMR (400 MHz, CDCl3)δ = 10.86 (br, 1H), 8.90 (dd, J=4.4, 1.6, 1H), 8.79 (dd, J=5.6, 3.2, 1H), 8.14 (dd, J=8.4, 1.6, 1H), 7.71 (dd, J=5.6, 3.0, 2H), 7.58 (dd, J=5.6, 3.0, 2H), 7.52-7.50 (m, 2H), 7.45 (dd, J=8.4, 4.4, 1H), 5.57 (d, J=13.6, 1H), 3.93 (d, J=13.6, 1H), 3.66 (s, 3H), 0.12 (s, 9H).

S19

NHO

N

N

GeMe3

O

O3b

NHO

N

N

GeMe3

O

O

OMe

3c

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-2.2

13

35.5

36

55.1

7759

.714

113.8

8611

7.387

121.

751

122.

208

123.

470

127.

376

128.

055

131.

472

132.

188

134.

067

134.

583

136.

263

148.

763

157.

329

167.

218

168.

263

13C NMR (101 MHz, CDCl3) δ = 168.26, 167.22, 157.33, 148.76, 138.93, 136.26, 134.58, 134.07, 132.19, 131.47, 128.06, 127.38, 123.47, 122.21, 121.75, 117.39, 113.89, 59.71, 55.18, 35.54, -2.21.

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.512.5f1 (ppm)

8.86

2.98

1.00

1.00

1.94

2.01

1.02

2.00

1.98

2.00

0.98

1.04

0.97

0.97

0.12

1

2.15

0

3.94

53.

979

5.59

35.

627

6.91

36.

933

6.97

0

7.51

1

8.12

58.

146

8.78

38.

792

8.79

78.

806

8.90

0

10.8

57

d.r. = 12.5:1 determined by 1H NMR. 1H NMR (400 MHz, CDCl3)δ = 10.86 (br, 1H), 8.90 (dd, J=4.4, 1.6, 1H), 8.79 (dd, J=5.6, 3.2, 1H), 8.14 (dd, J=8.4, 1.6, 1H), 7.70 (td, J=5.6, 2.4, 2H), 7.58 (dd, J=5.6, 3.2, 2H), 7.53-7.50 (m, 2H), 7.45 (dd, J=8.4, 4.4, 1H), 6.98 (d, J=8.0, 2H), 6.92 (d, J=8.0, 2H), 5.61 (d, J=13.6, 1H), 3.96 (d, J=13.6, 1H), 2.15 (s, 3H), 0.12 (s, 9H).

S20

NHO

N

N

GeMe3

O

O

OMe

3c

NHO

N

N

GeMe3

O

O

Me

3d

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-2.2

09

21.0

16

36.0

77

59.6

14

117.3

9412

1.75

412

2.20

212

3.47

212

7.38

312

8.06

112

9.14

013

1.52

213

4.00

613

4.59

813

4.73

913

6.26

114

8.76

9

167.

242

168.

253

13C NMR (101 MHz, CDCl3) δ = 168.25, 167.24, 148.77, 138.95, 136.93, 136.26, 134.74, 134.60, 134.01, 131.52, 129.14, 128.06, 127.38, 123.47, 122.20, 121.75, 117.39, 59.61, 36.08, 21.02, -2.21.

-2-1012345678910111213f1 (ppm)

9.04

3.12

2.05

1.03

1.02

2.00

2.04

1.03

2.02

2.03

2.01

1.00

1.03

1.00

0.97

0.12

6

1.01

91.

038

1.05

7

2.43

32.

452

3.93

33.

966

5.59

15.

625

6.92

06.

981

7.43

1

8.12

4

8.78

78.

801

8.89

48.

904

10.8

62

1H NMR (400 MHz, CDCl3) δ = 10.86 (br, 1H), 8.90 (dd, J=4.4, 1.6, 1H), 8.80 (dd, J=5.6, 3.2, 1H), 8.14 (dd, J=8.4, 1.6, 1H), 7.70 (dd, J=5.6, 3.2, 2H), 7.57 (dd, J=5.6, 3.2, 2H), 7.53-7.51 (m, 2H), 7.45 (dd, J=8.4, 4.4, 1H), 6.99 (d, J=8.4, 2H), 6.93 (d, J=8.0, 2H), 5.61 (d, J=13.6, 1H), 3.95 (d, J=13.6, 1H), 2.44 (d, J=7.6, 2H), 1.04 (t, J=7.6, 3H), 0.13 (s, 9H).

S21

NHO

N

N

GeMe3

O

O

Me

3d

NHO

N

N

GeMe3

O

O

Et

3e

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-2.1

74

15.4

37

28.3

35

36.1

46

59.6

91

117.3

9612

1.74

912

2.19

912

3.42

112

7.38

412

7.83

012

8.06

313

1.52

613

3.97

513

4.60

913

6.26

4

148.

771

167.

283

168.

301

13C NMR (101 MHz, CDCl3) δ = 168.30, 167.28, 148.77, 141.18, 138.95, 137.15, 136.26, 134.61, 133.98, 131.53, 128.06, 127.83, 127.38, 123.42, 122.20, 121.75, 117.40, 59.69, 36.15, 28.33, 15.44, -2.17.

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.512.5f1 (ppm)

9.86

1.23

1.00

2.04

3.10

1.05

2.08

1.91

2.06

1.05

1.00

1.02

0.91

3.98

34.

017

5.56

65.

599

6.96

97.

255

7.27

17.

457

7.51

7

7.72

18.

132

8.15

38.

762

8.77

48.

785

8.87

4

8.88

9

10.7

84

d.r. = 4:1 determined by 1H NMR. 1H NMR of main product (400 MHz, CDCl3) δ = 10.78 (br, 1H), 8.88 (dd, J=4.4, 1.6, 1H), 8.79-8.76 (m, 1H), 8.14 (dd, J=8.4, 1.6, 1H), 7.73 (dd, J=5.6, 3.2, 2H), 7.62 (dd, J=5.6, 3.2, 2H), 7.52 (d, J=4.0, 2H), 7.45 (dd, J=8.4, 4.4, 1H), 7.27-7.25 (m, 2H), 6.98 (d, J=8.4, 2H), 5.58 (d, J=13.6, 1H), 4.00 (d, J=13.6, 1H), 0.13 (s, 9H).

S22

NHO

N

N

GeMe3

O

O

Et

3e

NHO

N

N

GeMe3

O

O

Br

3f

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-2.2

15-2

.186

36.1

19

58.9

45

117.3

9311

9.034

121.

810

122.

330

123.

467

123.

634

127.

388

128.

065

128.

440

131.

359

131.

586

148.

792

166.

759

168.

186

13C NMR (101 MHz, CDCl3) δ = 168.19, 166.76, 148.79, 139.63, 138.89, 136.31, 134.44, 134.27, 134.07, 131.59, 131.36, 128.44, 128.07, 127.39, 123.63, 123.47, 122.33, 121.81, 119.03, 117.39, 58.95, 36.12, -2.19, -2.22.

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.512.5f1 (ppm)

9.01

1.02

1.05

2.01

2.02

1.02

2.03

2.00

1.01

1.04

1.00

0.99

0.13

7

3.96

74.

000

5.55

95.

593

6.80

76.

850

7.05

1

7.43

57.

597

8.13

18.

152

8.77

58.

784

8.78

88.

797

8.88

1

10.8

17

1H NMR (400 MHz, CDCl3) δ 10.82 (s, 1H), 8.88 (dd, J = 4.0, 1.6 Hz, 1H), 8.79 (dd, J = 5.2, 3.6 Hz, 1H), 8.14 (dd, J = 8.4, 1.6 Hz, 1H), 7.72 (dd, J = 5.6, 3.2 Hz, 2H), 7.61 (dd, J = 5.6, 3.2 Hz, 2H), 7.45

S23

NHO

N

N

GeMe3

O

O

Br

3f

NHO

N

N

GeMe3

O

O

F

3g

(dd, J = 8.4, 4.2 Hz, 1H), 7.05 (dd, J = 8.8, 5.2 Hz, 2H), 6.83 (t, J = 8.8 Hz, 2H), 5.58 (d, J = 13.6 Hz, 1H), 3.98 (d, J = 13.6 Hz, 1H), 0.14 (s, 9H).

-100102030405060708090100110120130140150160170180190200210

f1 (ppm)

-2.2

12

35.7

65

59.3

95

115.2

3311

5.444

117.3

8412

1.78

612

2.28

712

3.53

612

7.38

712

8.06

412

8.94

013

1.35

913

4.21

6

136.

299

148.

777

159.

638

162.

057

166.

900

168.

203

13C NMR (101 MHz, CDCl3) δ 168.20, 166.90, 160.85, 148.78, 138.91, 136.30, 136.12(d, J = 3.1 Hz),134.49, 134.22, 131.36, 128.94, 128.06, 127.39, 123.54, 122.04 (d, J = 50.1 Hz), 117.38, 115.33(d, J = 21.1 Hz), 59.39, 35.76, -2.21.

19F NMR (376 MHz, CDCl3) δ = -117.79.

S24

NHO

N

N

GeMe3

O

O

F

3g

NHO

N

N

GeMe3

O

O

F

3g

-2-1012345678910111213f1 (ppm)

9.00

3.04

1.01

1.00

0.07

1.03

2.07

2.01

2.06

1.00

1.03

0.98

1.00

0.14

8

3.71

33.

962

3.99

6

5.61

15.

645

6.49

86.

634

6.69

9

7.43

0

8.12

5

8.78

48.

798

8.88

78.

898

10.8

56

d.r. = 15:1 determined by 1H NMR. 1H NMR (400 MHz, CDCl3) δ = 10.86 (br, 1H), 8.89 (dd, J=4.4, 1.6, 1H), 8.80 (dd, J=5.6, 3.2, 1H), 8.14 (dd, J=8.4, 1.6, 1H), 7.71 (dd, J=5.6, 3.2, 2H), 7.58 (dd, J=5.6, 3.2, 2H), 7.53-7.51 (m, 2H), 7.45 (dd, J=8.4, 4.4, 1H), 5.73 (d, J=13.2, 0H), 5.63 (d, J=13.6, 1H), 3.98 (d, J=13.6, 1H), 3.71 (s, 3H), 0.15 (s, 9H).

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-2.1

27

36.7

55

55.2

4459

.368

111.6

5511

7.397

122.

234

127.

373

129.

378

134.

083

136.

271

148.

773

159.

556

167.

082

168.

225

13C NMR (101 MHz, CDCl3) δ = 168.23, 167.08, 159.56, 148.77, 141.90, 138.93, 136.27, 134.56, 134.08, 131.48, 129.38, 128.06, 127.37, 123.48, 122.23, 121.76, 117.40, 111.65, 59.37, 55.24, 36.75, -2.13.

S25

NHO

N

N

GeMe3

O

O

OMe

3h

NHO

N

N

GeMe3

O

O

OMe

3h

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.512.5f1 (ppm)

9.01

1.00

1.00

1.00

1.01

1.03

1.00

1.03

2.00

2.05

2.03

1.01

1.02

1.04

1.01

0.15

2

4.01

34.

046

5.58

75.

621

6.64

56.

687

6.82

66.

893

7.42

9

7.73

68.

124

8.14

48.

771

8.78

18.

784

8.79

4

8.88

2

10.8

01

d.r. = 14:1 determined by 1H NMR. 1H NMR (400 MHz, CDCl3) δ = 10.80 (br, 1H), 8.88 (dd, J=4.4, 1.6, 1H), 8.78 (dd, J=5.2, 4.0, 1H), 8.14 (dd, J=8.4, 1.6, 1H), 7.73 (dd, J=5.6, 3.1, 2H), 7.60 (dd, J=5.6, 3.2, 2H), 7.53-7.51 (m, 2H), 7.44 (dd, J=8.4, 4.2, 1H), 7.10 (td, J=8.0, 6.4, 1H), 6.88 (d, J=8.0, 1H), 6.82 (dt, J=10.0, 2.0, 1H), 6.67 (td, J=8.4, 2.0, 1H), 5.60 (d, J=13.5, 1H), 4.03 (d, J=13.6, 1H), 0.15 (s, 9H).

-100102030405060708090100110120130140150160170180190200210

f1 (ppm)

-2.1

67

36.5

92

59.0

24

112.2

6011

2.469

117.3

5912

2.30

712

7.35

612

9.85

213

1.35

513

4.43

2

148.

778

161.

591

164.

033

166.

754

168.

129

13C NMR (101 MHz, CDCl3) δ = 168.13, 166.75, 162.81 (d, J=244.2), 148.78, 143.27 (d, J=7.3), 138.87, 136.29, 134.43, 134.19, 131.36, 129.89, 128.04 (s, 3H), 127.36, 123.56, 122.31, 121.79, 117.36, 112.45 (d, J=21.1), 59.02, 36.59, -2.17

S26

NHO

N

N

GeMe3

O

O

F

3i

NHO

N

N

GeMe3

O

O

F

3i

19F NMR (376 MHz, CDCl3) δ = -112.97.

-1.00.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.512.5f1 (ppm)

8.67

1.01

0.99

1.95

0.98

1.00

2.03

2.02

2.13

0.25

1.00

0.94

0.96

0.91

0.19

9

4.32

04.

353

5.46

35.

496

6.71

86.

737

6.88

87.

437

7.61

88.

130

8.15

18.

771

8.78

28.

794

8.89

7

8.90

8

10.8

42

d.r. = 4:1 determined by 1H NMR. 1H NMR (400 MHz, CDCl3) δ = 10.84 (s, 1H), 8.90 (dd, J=4.4, 1.6, 1H), 8.78 (t, J=4.4, 1H), 8.14 (dd, J=8.4, 1.6, 1H), 8.07 (dd, J=8.4, 1.6, 0H), 7.77-7.74 (m, 2H), 7.62 (dd, J=5.6, 3.2, 2H), 7.52 (d, J=4.4, 2H), 7.45 (dd, J=8.4, 4.4, 1H), 6.88 (d, J=5.2, 1H), 6.76-6.72 (m, 2H), 5.48 (d, J=13.2, 1H), 4.34 (d, J=13.2, 1H), 0.20 (s, 9H).

S27

NHO

N

N

GeMe3

O

O

S

3j

NHO

N

N

GeMe3

O

O

F

3i

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-2.1

98

31.2

94

60.7

57

117.4

4612

1.78

512

2.30

912

2.34

112

3.56

412

3.91

912

4.13

212

6.81

612

7.36

412

8.06

513

1.52

213

4.15

414

8.80

7

166.

670

168.

201

13C NMR (101 MHz, CDCl3) δ = 168.20, 166.67, 148.81, 143.39, 138.93, 136.28, 134.50, 134.15, 131.52, 128.06, 127.36, 126.82, 124.13, 123.92, 123.56, 122.34, 122.31, 121.78, 117.45, 60.76, 31.29, -2.20.

-1.00.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.5f1 (ppm)

9.01

1.17

1.27

2.20

0.76

1.03

0.65

1.08

1.05

0.70

0.21

3.00

1.00

0.98

0.99

0.96

0.18

3

1.65

01.

685

1.87

11.

905

2.08

72.

159

2.32

53.

465

3.51

43.

581

3.85

04.

061

4.52

94.

870

4.89

0

5.83

9

7.26

07.

421

7.44

37.

471

8.10

5

8.67

78.

708

8.80

1

10.2

6010

.333

d.r. = 2.4:1 determined by 1H NMR.1H NMR(400 MHz, CDCl3) δ = 10.27 (s, 1H), 8.81-8.79 (m, 1H), 8.72-8.68 (m, 1H), 8.12 (dd, J=8.4, 1.6, 1H), 7.54-7.40 (m, 3H), 5.84 (s, 0.21 H), 4.88 (d, J=8.4, 1H), 4.12-3.85 (m, 1H), 3.80 (s, 0.65 H), 3.61-3.47 (m, 1H), 2.38-2.27 (m, 0.76 H), 2.16 (s, 2H), 2.09 (s, 1H), 1.93-1.63 (m, 1H), 0.18 (s, 9H).

S28

NHO

GeMe3

N

NAc

3k

NHO

N

N

GeMe3

O

O

S

3j

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-2.6

47-2

.402

22.6

2622

.868

26.0

0427

.933

31.9

2734

.020

47.4

38

56.5

84

64.0

1966

.580

107.

519

116.5

7412

1.66

512

7.31

013

3.62

313

6.27

713

8.59

614

8.46

714

8.97

2

157.

416

169.

874

169.

903

170.

321

186.

952

13C NMR (101 MHz, CDCl3) δ = 186.95, 170.32, 169.90, 169.87, 157.42, 148.97, 148.47, 138.69, 138.60, 136.38, 136.28, 134.43, 133.62, 128.03, 127.38, 127.31, 122.36, 121.95, 121.70, 121.67, 116.61, 116.57, 107.52, 66.58, 64.02, 56.58, 48.73, 47.44, 34.02, 31.93, 27.93, 26.00, 22.87, 22.63, -2.40, -2.65.

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.5f1 (ppm)

-1000

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

10000

11000

120009.

00

1.02

1.00

1.00

8.29

0.98

1.93

0.97

0.05

0

1.48

21.

505

1.51

71.

540

1.72

31.

740

1.75

71.

774

3.82

83.

846

3.85

13.

869

7.24

07.

255

7.27

67.

332

7.35

27.

370

7.38

27.

393

7.49

08.

089

8.09

28.

109

8.73

68.

741

8.74

68.

755

9.93

4

1H NMR (400 MHz, CDCl3) δ 9.93 (br, 1H),8.76- 8.74 (m, 2H), 8.10 (dd, J = 8.0, 1.6 Hz, 1H), 7.51-7.24 (m, 8H), 3.85 (dd, J = 9.2, 7.2 Hz, 1H), 1.75 (dd, J = 13.6, 6.8 Hz, 1H), 1.51 (dd, J = 13.6, 9.2 Hz, 1H), 0.05 (s, 9H).

S29

NHO

GeMe3

N

NAc

3k

ON

HN

GeMe3

5a

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-1000

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

10000

11000

12000

13000

-1.7

29

21.3

90

51.8

12

116.

401

121.

461

127.

446

134.

760

138.

642

148.

263

173.

181

13C NMR (101 MHz, CDCl3) δ 173.18, 148.26, 141.57, 138.64, 136.36, 134.76, 128.97, 128.09, 128.01, 127.51, 127.45, 121.62, 121.46, 116.40, 51.81, 21.39, -1.73

-10123456789101112f1 (ppm)

-1000

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

10000

11000

12000

9.07

1.01

1.00

3.04

0.99

3.15

0.99

3.04

1.00

0.96

0.98

0.98

0.07

3

1.47

51.

497

1.50

91.

532

1.76

21.

780

2.51

5

4.09

04.

111

4.13

0

7.17

07.

233

7.35

97.

379

7.42

57.

470

7.54

5

8.07

78.

095

8.67

88.

685

8.74

59.

874

1H NMR (400 MHz, CDCl3) δ 9.87 (br, 1H), 8.74 (d, J = 7.4 Hz, 1H), 8.68 (d, J = 2.8 Hz, 1H), 8.09 (d, J = 7.2 Hz, 1H), 7.55-7.43 (m, 3H), 7.37 (dd, J = 8.0, 4.0 Hz, 1H), 7.25-7.17 (m, 3H), 4.11 (dd, J = 8.4, 7.6 Hz, 1H), 2.52 (s, 3H), 1.79 (dd, J = 13.6, 7.2 Hz, 1H), 1.50 (dd, J = 13.6, 9.2 Hz, 1H), 0.07 (s, 9H).

S30

ON

HN

GeMe3

5a

ON

HN

GeMe3

Me 5b

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-500

0

500

1000

1500

2000

2500

3000

3500

4000

4500

-1.5

89

20.1

6820

.727

47.2

97

116.

311

121.

383

126.

803

127.

540

139.

570

148.

240

173.

322

13C NMR (101 MHz, CDCl3) δ 173.32, 148.24, 139.57, 138.62, 136.31, 135.91, 134.81, 130.95, 127.98, 127.54, 127.50, 127.24, 126.80, 121.58, 121.38, 116.31, 47.30, 20.73, 20.17, -1.59

-2-1012345678910111213f1 (ppm)

-1000

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

10000

11000

12000

13000

14000

15000

16000

17000

9.03

1.04

1.04

1.01

1.02

1.08

4.05

1.03

1.00

0.96

0.94

0.92

0.08

9

1.47

11.

492

1.50

51.

526

1.58

41.

716

1.73

51.

750

1.76

9

4.47

24.

492

4.51

2

7.16

57.

259

7.38

27.

419

7.46

87.

495

8.10

18.

121

8.72

98.

747

8.76

88.

778

10.0

70

1H NMR (400 MHz, CDCl3) δ 10.07 (br, 1H), 8.77 (dd, J = 4.0, 1.6 Hz, 1H), 8.74 (dd, J = 7.2, 1.6 Hz, 1H), 8.11 (dd, J = 8.0, 1.2 Hz, 1H), 7.63 (d, J = 7.6 Hz, 1H), 752-7.38 (m, 4H), 7.29 (d, J = 7.6 Hz, 1H),

S31

ON

HN

GeMe3

Me 5b

ON

HN

GeMe3

Cl 5c

7.18 (t, J = 7.6 Hz, 1H), 4.49 (t, J = 8.0 Hz, 1H), 1.74 (dd, J = 13.6, 7.6 Hz, 1H), 1.50 (dd, J = 13.6, 8.4 Hz, 1H), 0.09 (s, 9H).

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-1000

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

10000

11000

12000

13000

14000

15000

-1.6

75

20.6

27

46.6

70

116.

510

121.

585

127.

457

128.

005

129.

191

136.

296

148.

393

172.

190

13C NMR (101 MHz, CDCl3) δ 172.19, 148.39, 139.16, 138.64, 136.30, 134.82, 133.60, 129.72, 129.19, 128.47, 128.01, 127.55, 127.46, 121.68, 121.59, 116.51, 46.67, 20.63, -1.68

-2-10123456789101112f1 (ppm)

-1000

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

10000

11000

12000

13000

14000

15000

9.07

1.03

1.03

0.96

0.97

1.03

0.92

1.01

2.08

1.05

1.00

2.07

0.99

0.07

9

1.47

91.

501

1.51

31.

535

1.72

61.

744

1.76

01.

778

4.24

94.

270

4.28

9

7.04

97.

141

7.21

27.

260

7.41

97.

469

7.49

8

8.10

58.

125

8.74

18.

759

8.77

2

10.0

44

1H NMR (400 MHz, CDCl3) δ 10.04 (br, 1H), 8.78-8.74 (m, 2H), 8.11 (d, J = 8.0 Hz, 1H), 7.58 (t, J = 6.8 Hz, 1H), 7.52-7.45 (m, 2H), 7.41 (dd, J = 8.0, 4.0 Hz, 1H), 7.24-7.21 (m, 1H), 7.16 (t, J = 7.2 Hz,

S32

ON

HN

GeMe3

Cl 5c

ON

HN

GeMe3

F 5d

1H), 7.07 (t, J = 7.2 Hz, 1H), 4.27 (dd, J = 8.4, 7.6 Hz, 1H), 1.75 (dd, J = 13.6, 7.2 Hz, 1H), 1.51 (dd, J = 13.6, 8.8 Hz, 1H), 0.08 (s, 9H).

-100102030405060708090100110120130140150160170180190200210

f1 (ppm)

-500

0

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

5500

6000

6500

7000-1.8

05

20.1

67

43.0

1343

.039

115.

502

115.

728

116.

519

121.

587

128.

453

134.

743

136.

321

148.

379

159.

195

161.

627

172.

282

13C NMR (101 MHz, CDCl3) δ 172.28, 161.41 (d, J = 243.2 Hz), 148.38, 138.65, 136.32, 134.74, 129.36 (d, J = 3.8 Hz), 128.84 (d, J = 8.3 Hz), 128.52 (d, J = 14.6 Hz),128.01, 127.46, 124.74 (d, J = 3.5 Hz), 121.63 (d, J = 8.3 Hz), 116.52, 115.73, 115.50, 43.03 (d, J = 2.6 Hz), 20.17, -1.81.

19F NMR (376 MHz, CDCl3) δ = -118.12.

S33

ON

HN

GeMe3

F 5d

ON

HN

GeMe3

F 5d

-1.00.01.02.03.04.05.06.07.08.09.010.011.012.0f1 (ppm)

-2000

0

2000

4000

6000

8000

10000

12000

14000

16000

18000

20000

22000

24000

26000

9.00

1.00

1.04

1.00

2.16

5.05

1.00

1.02

0.97

0.97

0.07

8

1.43

01.

452

1.46

51.

486

1.70

81.

727

1.74

31.

761

3.80

63.

826

3.84

6

7.22

67.

242

7.25

17.

276

7.38

17.

406

7.42

77.

454

7.51

78.

110

8.11

48.

131

8.71

78.

735

8.76

68.

776

9.95

5

1H NMR (400 MHz, CDCl3) δ 9.96 (br, 1H), 8.77 (dd, J = 4.0, 1.6 Hz, 1H), 8.73 (dd, J = 7.2, 1.6 Hz, 1H), 8.12 (dd, J = 8.4, 1.6 Hz, 1H), 7.52-7.38 (m, 5H), 7.30-7.23 (m, 2H), 3.83 (t, J = 8.0 Hz, 1H), 1.73 (dd, J = 13.6, 7.2 Hz, 1H), 1.46 (dd, J = 13.6, 8.8 Hz, 1H), 0.08 (s, 9H).

-100102030405060708090100110120130140150160170180190200210

f1 (ppm)

-500

0

500

1000

1500

2000

2500

3000

3500

4000

4500-1

.697

21.5

24

51.4

73

116.

624

121.

716

126.

273

128.

037

134.

491

143.

723

148.

323

172.

354

13C NMR (101 MHz, CDCl3) δ 172.35, 148.32, 143.72, 138.54, 136.52, 134.74, 134.49, 130.15,

128.19, 128.04, 127.62, 127.52, 126.27, 121.72, 116.62, 51.47, 21.52, -1.70.

S34

ON

HN

GeMe3Cl

5e

ON

HN

GeMe3Cl

5e

-1.5-0.50.51.52.53.54.55.56.57.58.59.510.511.512.5f1 (ppm)

8.99

1.06

1.04

1.02

1.00

3.47

1.02

2.05

1.00

1.00

0.99

0.95

0.07

4

1.44

31.

465

1.47

71.

499

1.70

71.

725

1.74

1

3.82

53.

844

3.86

5

6.93

26.

961

6.98

27.

258

7.30

17.

340

7.48

58.

111

8.72

38.

741

8.76

99.

948

1H NMR (400 MHz, CDCl3) δ = 9.95 (br, 1H), 8.77 (dd, J=4.4, 1.6, 1H), 8.73 (dd, J=7.2, 1.6, 1H), 8.12

(dd, J=8.4, 1.6, 1H), 7.52-7.46 (m, 2H), 7.42 (dd, J=8.4, 4.4, 1H), 7.34-7.22 (m, 3H), 6.98-6.93 (m,

1H), 3.84 (dd, J=8.4, 7.6, 1H), 1.73 (dd, J=13.6, 7.2, 1H), 1.47 (dd, J=13.7, 8.8, 1H), 0.07 (s, 9H).

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-1.7

23

21.4

39

51.5

1251

.527

114.2

7011

4.479

114.8

7411

5.090

116.5

0012

1.67

312

3.78

112

7.50

1

136.

430

144.

136

144.

206

148.

358

161.

992

172.

455

13C NMR (101 MHz, CDCl3) δ = 172.45, 164.44, 161.99, 148.36, 144.21, 144.14, 138.61, 136.43,

S35

ON

HN

GeMe3F

5f

ON

HN

GeMe3F

5f

134.56, 130.41, 130.33, 128.03, 127.50, 123.81, 123.78, 121.71, 121.67, 116.50, 115.09, 114.87,

114.48, 114.27, 51.53, 51.51, 21.44, -1.72.

19F NMR (376 MHz, CDCl3) δ = -112.59.

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.5f1 (ppm)

9.01

1.05

1.05

1.02

1.97

5.00

1.00

1.00

0.97

0.98

0.05

9

1.45

01.

473

1.48

41.

507

1.69

91.

716

1.73

31.

750

3.81

83.

835

3.84

13.

859

7.01

57.

023

7.02

87.

040

7.04

5

7.06

77.

405

7.46

48.

110

8.11

48.

130

8.72

38.

741

8.75

28.

763

9.92

6

S36

ON

HN

GeMe3

F 5g

ON

HN

GeMe3F

5f

1H NMR (400 MHz, CDCl3) δ = 9.93 (br, 1H), 8.76 (dd, J=4.4, 1.6, 1H), 8.73 (dd, J=7.2, 1.6, 1H), 8.12 (dd, J=8.4, 1.6, 1H), 7.52-7.41 (m, 5H), 7.07-7.02 (m, 2H), 3.84 (dd, J=9.2, 6.8, 1H), 1.72 (dd, J=13.6, 6.8, 1H), 1.48 (dd, J=13.6, 9.2, 1H), 0.06 (s, 9H).

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-1.7

14

21.6

05

51.0

05

115.6

5211

5.864

116.4

6312

1.62

612

7.50

4

134.

600

148.

329

161.

045

163.

486

173.

031

13C NMR (101 MHz, CDCl3) δ = 173.03, 163.49, 161.05, 148.33, 138.61, 137.36, 137.32, 136.44, 134.60, 129.63, 129.55, 128.03, 127.50, 121.69, 121.63, 116.46, 115.86, 115.65, 51.00, 21.61, -1.71.

19F 19F NMR (376 MHz, CDCl3) δ = -115.46.

S37

ON

HN

GeMe3

F 5g

ON

HN

GeMe3

F 5g

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.5f1 (ppm)

8.93

1.00

1.03

1.01

1.01

1.98

1.99

1.95

1.00

0.90

0.97

0.95

0.17

7

1.77

81.

792

1.81

21.

826

2.17

12.

200

2.20

42.

234

5.20

95.

222

5.23

95.

252

7.41

27.

433

7.49

37.

733

7.74

67.

883

7.89

78.

704

8.71

68.

727

8.74

58.

749

10.4

75

1H NMR (400 MHz, CDCl3) δ = 10.47 (br, 1H), 8.75 (dd, J=4.4, 1.6, 1H), 8.72 (t, J=4.4, 1H), 8.14 (dd, J=8.4, 1.6, 1H), 7.89 (dd, J=5.2, 3.2, 2H), 7.74 (dd, J=5.2, 3.2, 2H), 7.50 (d, J=4.4, 2H), 7.43 (dd, J=8.4, 4.4, 1H), 5.23 (dd, J=12.0, 5.6, 1H), 2.20 (dd, J=13.6, 12.0, 1H), 1.80 (dd, J=13.6, 5.6, 1H), 0.18 (s, 9H).

13C -100102030405060708090100110120130140150160170180190200210

f1 (ppm)

-1.7

32

21.6

71

51.6

26

116.5

4912

1.76

612

2.89

812

4.30

112

4.37

612

4.84

812

4.92

312

7.48

012

8.31

413

0.74

013

1.37

913

1.69

913

6.45

114

8.37

4

172.

217

NMR (101 MHz, CDCl3) δ = 172.22, 148.37, 142.66, 138.60, 136.45, 134.44, 131.54,131.22 (q, J=32.0), 129.39, 128.03, 127.48, 124.87 (q, J=3.8), 124.32 (q, J=3.8), 124.25 (q, J=270.8), 121.78 (d, J=1.8), 116.55, 51.63, 21.67, -1.73.

S38

ON

HN

GeMe3

F3C 5h

ON

HN

GeMe3

F3C 5h

19F NMR (376 MHz, CDCl3) δ = -62.52.

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.5f1 (ppm)

9.01

1.02

1.05

1.00

5.03

0.98

1.00

1.02

0.99

0.96

0.09

7

1.39

11.

412

1.42

51.

446

1.70

11.

721

1.73

61.

755

3.78

13.

801

3.82

1

7.33

97.

360

7.40

77.

441

7.46

27.

496

7.51

37.

618

8.13

28.

152

8.70

18.

718

8.78

68.

797

9.95

3

1H NMR (400 MHz, CDCl3) δ = 9.95 (br, 1H), 8.79 (dd, J=4.4, 1.6, 1H), 8.71 (dd, J=6.8, 2.4, 1H), 8.14 (dd, J=8.0, 1.6, 1H), 7.62 (d, J=2.0, 1H), 7.53-7.34 (m, 5H), 3.80 (t, J=8.0, 1H), 1.73 (dd, J=13.6, 8.0, 1H), 1.42 (dd, J=13.6, 8.4, 1H), 0.10 (s, 9H).

S39

ON

HN

GeMe3Cl

Cl 5i

ON

HN

GeMe3

F3C 5h

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-1.6

42

21.6

03

50.9

87

116.6

0212

1.79

512

7.39

812

8.05

013

0.78

4

136.

512

148.

438

171.

925

13C NMR (101 MHz, CDCl3) δ = 171.92, 148.44, 142.05, 138.57, 136.51, 134.38, 132.89, 131.45, 130.78, 129.97, 128.05, 127.50, 127.40, 121.86, 121.79, 116.60, 50.99, 21.60, -1.64.

-2-10123456789101112f1 (ppm)

-500

0

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

5500

6000

9.05

1.02

1.01

1.00

1.00

4.05

1.04

3.03

1.05

1.00

1.00

1.05

1.00

0.08

3

1.59

01.

612

1.62

41.

647

1.83

81.

856

1.87

21.

890

4.03

14.

051

4.07

1

7.26

07.

357

7.37

87.

442

7.46

57.

480

7.51

27.

661

7.82

27.

856

8.66

08.

670

8.75

48.

773

10.0

15

1H NMR (400 MHz, CDCl3) δ 10.01 (br, 1H), 8.76 (d, J = 7.6 Hz, 1H), 8.67 (d, J = 4.0 Hz, 1H), 8.07 (d, J = 8.4 Hz, 1H), 7.96 (s, 1H), 7.88-7.80 (m, 3H), 7.65 (d, J = 8.4 Hz, 1H), 7.51-7.42 (m, 4H), 7.36 (dd, J = 8.0, 4.0 Hz, 1H), 4.05 (t, J = 8.0 Hz, 1H), 1.86 (dd, J = 13.6, 7.2 Hz, 1H), 1.62 (dd, J = 13.6, 8.8 Hz, 1H), 0.08 (s, 9H).

S40

ON

HN

GeMe3

5j

ON

HN

GeMe3Cl

Cl 5i

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-500

0

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

-1.6

22

21.3

47

51.9

29

116.

399

121.

491

126.

095

127.

470

127.

972

139.

150

148.

242

173.

037

13C NMR (101 MHz, CDCl3) δ 173.04, 148.24, 139.15, 138.60, 136.32, 134.70, 133.76, 132.89, 128.75, 127.97, 127.95, 127.79, 127.47, 126.79, 126.26, 126.10, 125.88, 121.59, 121.49, 116.40, 51.93, 21.35, -1.62

-2-101234567891011121314f1 (ppm)

9.07

1.02

1.01

1.03

3.01

1.02

2.02

1.00

1.99

0.96

0.15

5

3.35

03.

373

5.51

55.

538

6.89

56.

934

7.13

27.

465

8.13

9

8.83

78.

844

8.84

8

8.85

9

10.9

53

1H NMR (400 MHz, CDCl3) δ = 10.95 (s, 1H), 8.86-8.84 (m, 2H), 8.15 (dd, J=8.4, 1.6, 1H), 7.58-7.53 (m, 2H), 7.45 (dd, J=8.4, 4.4, 1H), 7.15-7.05 (m, 3H), 6.91 (td, J=7.6, 0.8, 1H), 5.53 (d, J=9.2, 1H), 3.36 (d, J=9.2, 1H), 0.15 (s, 9H).

S41

ON

HN

GeMe3

5j

NH

O

GeMe3

N

O

5k

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-1.7

51

36.6

34

86.0

80

110.0

4811

6.910

121.

843

123.

598

127.

383

130.

963

136.

266

148.

801

157.

728

168.

518

13C NMR (101 MHz, CDCl3) δ = 168.52, 157.73, 148.80, 138.95, 136.27, 133.90, 130.96, 128.15, 127.38, 126.95, 123.60, 122.33, 121.84, 121.73, 116.91, 110.05, 86.08, 36.63, -1.75.

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.512.5f1 (ppm)

9.01

2.05

1.04

1.02

1.00

0.97

1.03

2.03

1.00

0.99

1.01

0.93

0.23

5

1.82

01.

844

1.85

91.

866

1.88

62.

043

2.10

03.

842

3.85

83.

867

3.88

7

4.42

94.

438

4.45

34.

464

4.47

34.

730

7.42

77.

437

7.44

77.

458

7.49

0

7.51

18.

132

8.15

38.

755

8.76

28.

771

8.77

8

8.85

4

10.8

16

1H NMR (400 MHz, CDCl3) δ = 10.82 (br, 1H), 8.85 (dd, J=4.4, 1.6, 1H), 8.77 (dd, J=6.4, 2.8, 1H), 8.14 (dd, J=8.4, 1.6, 1H), 7.55-7.49 (m, 2H), 7.44 (dd, J=8.4, 4.4, 1H), 4.74-4.72 (m, 1H), 4.47-4.43 (m, 1H), 3.90-3.84 (m, 1H), 2.12-2.04 (m, 1H), 1.91-1.82 (m, 2H), 0.23 (s, 9H).

S42

NH

O

GeMe3

N

O

5k

NH

O

GeMe3

N

O

5l

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-1.7

76

28.5

3432

.620

69.5

69

82.2

06

116.4

6812

1.69

712

7.41

513

4.17

313

6.26

3

148.

744

171.

649

13C NMR (101 MHz, CDCl3) δ = 171.65, 148.74, 139.04, 136.26, 134.17, 128.16, 127.42, 121.88, 121.70, 116.47, 82.21, 69.57, 32.62, 28.53, -1.78.

1H NMR (400 MHz, CDCl3) δ 7.90 – 7.84 (m, 2H), 7.77 – 7.71 (m, 2H), 4.97 (dd, J = 11.1, 5.7 Hz,

1H), 3.72 (s, 3H), 1.80 (dd, J = 14.1, 11.1 Hz, 1H), 1.69 (dd, J = 14.1, 5.7 Hz, 1H), 0.10 (s, 9H).

S43

NH

O

GeMe3

N

O

5l

OMeN

O

Me3Ge

O O

3ab

13C NMR (101 MHz, CDCl3) δ = 170.87, 167.42, 134.02, 131.71, 123.34, 52.65, 49.85, 16.98, -2.23.

1H NMR (501 MHz, CDCl3) δ 8.93 (d, J = 7.5 Hz, 1H), 8.18 (s, 1H), 8.00 (d, J = 8.0 Hz, 1H), 7.83 (s, 2H), 7.68 (s, 2H), 7.40 (t, J = 8.0 Hz, 1H), 7.19 (d, J = 7.5 Hz, 1H), 7.15 (dd, J = 7.5, 4.5 Hz, 1H), 5.32 (t, J = 10.0 Hz, 1H), 2.40(t, J = 9.0 Hz, 1H)2.32 (s, 3H),1.95(t, J = 8.0 Hz, 1H).

S44

OMeN

O

Me3Ge

O O

3ab