Supporting Information: Ester with Alcohols via …S1 Supporting Information: Manganese-Catalyzed...

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S1 Supporting Information: Manganese-Catalyzed Direct C-C Coupling of α-C−H bonds of Amides and Ester with Alcohols via Hydrogen Autotransfer Ekambaram Balaraman* a Jagannath Rana, b,c Virendrakumar Gupta* d a Department of Chemical Sciences, Indian Institute of Science Education and Research – Tirupati (IISER-T), Tirupati 517507, India. b Organic Chemistry Division, CSIR-National Chemical Laboratory (CSIR-NCL), Dr. Homi Bhabha Road, Pune 411008, India. c Academy of Scientific and Innovative Research (AcSIR), Ghaziabad - 201002, India. d Polymer Synthesis & Catalysis, Reliance Research & Development Centre, Reliance Industries Limited, Ghansoli 400701, Navi Mumbai, India. Table of Content 1. Experimental section S2-S4 2. Mechanistic investigations S4-S8 3. Diversification of C-alkylated amides S8-S9 4. Characterization data of compounds S9-S16 5. Copies of NMR spectra S17-S41 6. HRMS Data S42-S51 Electronic Supplementary Material (ESI) for Dalton Transactions. This journal is © The Royal Society of Chemistry 2019

Transcript of Supporting Information: Ester with Alcohols via …S1 Supporting Information: Manganese-Catalyzed...

Page 1: Supporting Information: Ester with Alcohols via …S1 Supporting Information: Manganese-Catalyzed Direct C-C Coupling of α-C−H bonds of Amides and Ester with Alcohols via Hydrogen

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Supporting Information:

Manganese-Catalyzed Direct C-C Coupling of α-C−H bonds of Amides and

Ester with Alcohols via Hydrogen Autotransfer

Ekambaram Balaraman*a Jagannath Rana,b,c Virendrakumar Gupta*d

a Department of Chemical Sciences, Indian Institute of Science Education and Research –

Tirupati (IISER-T), Tirupati 517507, India.

b Organic Chemistry Division, CSIR-National Chemical Laboratory (CSIR-NCL), Dr. Homi

Bhabha Road, Pune 411008, India.

c Academy of Scientific and Innovative Research (AcSIR), Ghaziabad - 201002, India.

d Polymer Synthesis & Catalysis, Reliance Research & Development Centre, Reliance

Industries Limited, Ghansoli 400701, Navi Mumbai, India.

Table of Content

1. Experimental section S2-S4

2. Mechanistic investigations S4-S8

3. Diversification of C-alkylated amides S8-S9

4. Characterization data of compounds S9-S16

5. Copies of NMR spectra S17-S41

6. HRMS Data S42-S51

Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2019

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1 Experimental Section

1a. General Information

All catalytic experiments were carried out using standard Schlenk techniques. Unless

otherwise stated reaction were conducted in flame-dried glassware under an atmosphere of

nitrogen and commercially obtained reagent were used as received. All solvents were reagent

grade or better. Toluene was refluxed over sodium/benzophenone, followed by distilled under

argon atmosphere and stored over sodium. Chemicals used in catalysis reactions were used

without additional purification. Thin layer chromatography (TLC) was performed using silica

gel precoated aluminium foil which was visualized with visualized with UV light at 254 nm

or under iodine. Column chromatography was performed with SiO2 (Silicycle Siliaflash F60

(230-400 mesh). 1H NMR (500, 200 MHz), 13C NMR (126, 50 MHz) spectra were recorded

on the NMR spectrometer. Deuterated chloroform was used as the solvent, and chemical shift

values (δ) are reported in parts per million relative to the residual signals of this solvent [δ

7.27 for 1H (chloroform-d), δ 77.2 for 13C{1H} (chloroform-d). Abbreviations used in the

NMR follow-up experiments: s, singlet; d, doublet; dd, doublet of doublet; t, triplet; tt, triplet

of triplet; td, triplet of doublet; q, quartet; br, broad; m, multiplet. GC analysis was carried out

using a HP-5 column (30 m, 0.25 mm, 0.25μ). Mass spectra were obtained on a GCMS-QP

5000 instruments with ionization voltages of 70 eV. High resolution mass spectra (HRMS)

were obtained on a High-resolution mass spectra (HRMS) were obtained by fast atom

bombardment (FAB) using a double focusing magnetic sector mass spectrometer and electron

impact (EI) ionization technique (magnetic sector-electric sector double focusing mass

analyzer).

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1b. Complexes used for the present study

In a three-necked round-bottom flask (100 mL) under an argon atmosphere, Mn(CO)5Br (1.0

equivalents) was added in toluene. After that, PNP pincer ligand (1.05 equivalents) was

added drop by drop via syringe at room temperature. After stirring, the reaction mixture was

heated to 100 °C for 20 h. During that time the reaction mixture became an orange solution.

After cooling down to room temperature and removing the solvent at reduced pressure, led to

a yellow solid. Washing this solid with heptane (2 x 10 mL) and drying under high vacuum

provided the corresponding manganese complexes. The synthetic procedure for the complex

was followed from this literature, matches the data with literature value. [M. Peña-López, P.

Piehl, S. Elangovan, H. Neumann, M. Beller, Angew. Chem. Int. Ed. 2016, 55, 14967.]

N PCy2

PCy2

H

MnCO

CO

Br

Ia

N PtBu2

PtBu2

H

MnCO

CO

Br

Ib

N PPh2

PPh2

H

MnCO

CO

Br

Ic

1c. General experimental procedure for Mn-catalyzed C-alkylation of amides

In a 10 mL oven dried sealed tube, alcohol 2 (0.5 mmol, 1 equiv), and amide 1 (1.0 mmol, 2

equiv), manganese complex [Mn]-Ia (0.5 mol%), KOtBu (0.6 mmol, 1.2 equiv) were added

under an argon atmosphere in toluene (1.0 mL). The flask was sealed with a teflon plug under

an argon atmosphere, and the solution stirred at 110 oC for 16 hours. Then the reaction

mixture was cooled to room temperature, and the reaction mixture was quenched with water

(20 mL) and extracted with dichloromethane (2 x 20 mL). The entire organic layer was

combined, washed with brine (20 mL) and then dried over Na2SO4. After concentration under

reduced pressure, residue was purified by 250-400 mesh silica-gel column chromatography

using ethyl acetate/petroleum ether (1:3) to afford the pure product 3.

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1d. General experimental procedure for Mn-catalyzed C-alkylation of tert-butyl acetate

In a 10 mL oven dried sealed tube, alcohol 2 (0.5 mmol, 1 equiv), and tert-butyl acetate 1a’

(1.0 mmol, 2 equiv), manganese complex [Mn]-Ia (0.5 mol%), KOtBu (0.6 mmol, 1.2 equiv)

were added under an argon atmosphere in toluene (1.0 mL). The flask was sealed with a

teflon plug under an argon atmosphere, and the solution stirred at 80 oC for 12 hours. Then

the reaction mixture was cooled to room temperature, and the reaction mixture was quenched

with water (20 mL) and extracted with dichloromethane (2 x 20 mL). The entire organic layer

was combined, washed with brine (20 mL) and then dried over Na2SO4. After concentration

under reduced pressure, residue was purified by 250-400 mesh silica-gel column

chromatography using ethyl acetate/petroleum ether (1:3) to afford the pure product 5.

2. Mechanistic investigations

2a. Detection of H2 gas liberation

The evolution of H2 gas during the alkylation process was qualitatively observed using GC

analysis which reveals the reaction takes place via Mn-catalyzed auto hydrogen transfer

pathway.

OH

O

NMe

Me+ Standard conditions H2

1a 2a

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H2

Figure S1. GC analysis.

2b. Intermediate Determination

An,-unsaturated amide8 was applied under standard catalytic conditions in the presence

of benzyl alcohol 2h as hydrogen donor. The GC analysis of crude mixture showed the

formation of -alkylated amide and the corresponding dehydrogenated product (aldehyde) of

2h which confirmed the formation of enone (8) as a key intermediate in the catalytic process.

H

O

N Me

Me+

KOtBu (1.5 eq) N

OMe

Me

O

N

OMe

Me[Mn]-1a (0.5 mol%)

KOtBu (1.2 eq.)Toluene, 110 oC

N

OMe

Me

Cl Cl

Cl Cl

8

8 3h

1a (90%)THF, rt

+

O

H

Cl

2h (2 equiv)

(a)

(b)

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2c. Deuterium experiment

a) To a 15 mL clean and oven-dried screw cap reaction tube, 1a or 8 (1.0 mmol) and 2h-

[d] (96%) (0.5 mmol) were added under standard reaction conditions. Then the reaction was

performed under standard condition for 16 h. The percentage of deuterium incorporation in

the product was calculated based on HRMS analysis.

OH/D

DD

Cl

+ standard condtions N

OMe

MeCl

D/H

3h-d13h-d2

D/H = 46%D/D = 54%

1a or 8

2h-[d]

D D/H

J-92 #288 RT: 1.28 AV: 1 NL: 3.31E7T: FTMS + p ESI Full ms [100.0000-1500.0000]

210.0 210.5 211.0 211.5 212.0 212.5 213.0 213.5 214.0 214.5 215.0 215.5m/z

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

ativ

e A

bund

ance

211.0740R=77006

C 11 H12 2H O N Cl = 211.0743-1.3012 ppm

214.0959R=77006

C 11 H13 2H2 O N Cl = 214.0962-1.4963 ppm

213.0896R=77302

C 11 H12 2H2 O N Cl = 213.08845.5729 ppm

215.0866R=76502212.0648

R=76202

214.9171R=75702

210.9890R=60600

D

N

O

Cl

D

N

O

ClD

Figure S2. HRMS data for deuterium incorporation.

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2d. Parallel and competition experiments

To a 15 mL clean and oven-dried screw cap reaction tube, 1a (1.0 mmol) and 2h (0.5 mmol),

2h-[d] (96%) (0.5 mmol) were added under standard reaction conditions. Then the reaction

was carried out for 16 h. The percentage of deuterium incorporation in the product was

calculated based on HRMS analysis.

OH/D

DD

Cl

+standard condtions

D

N

OMe

MeCl

N

OMe

MeCl

3h-d1

3h

D/H = 35%

H/H = 65%1a

2h-[d]

+

OH

HH

Cl 2h

J-93 #275 RT: 1.22 AV: 1 NL: 4.10E8T: FTMS + p ESI Full ms [100.0000-1500.0000]

211 212 213 214 215 216 217 218 219 220 221 222 223 224m/z

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

ativ

e A

bund

ance

212.0827R=78002

C 11 H15 O N Cl = 212.0837-4.4815 ppm

213.0889R=75206

214.0803R=77402

215.0869R=74502

216.0929R=72200

219.1741R=73607

220.9344R=71502

220.1122R=70602

211.1596R=56900

217.0962R=59600

218.1177R=37100

N

OMe

MeCl

N

OMe

MeCl

D

Figure S3. HRMS data for deuterium incorporation.

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2e. Homogeneous nature of Mn-catalysis

In a 10 mL oven dried sealed tube, 2b (0.5 mmol, 1 equiv), 1a (1.0 mmol, 2 equiv),

manganese complex [Mn]-Ia (0.5 mol%), KOtBu (0.6 mmol, 1.2 equiv), and Hg (1 drop)

were added under an argon atmosphere in toluene (1.0 mL). The flask was sealed with a

teflon plug under an argon atmosphere, and the solution stirred at 110 oC for 16 hours. Then

the reaction mixture was cooled to room temperature, and the reaction mixture was quenched

with water (20 mL) and extracted with dichloromethane (2 x 20 mL). The entire organic layer

was combined, washed with brine (20 mL) and then dried over Na2SO4. After concentration

under reduced pressure, residue was purified by 250-400 mesh silica-gel column

chromatography using ethyl acetate/petroleum ether (1:3) to afford C-alkylated amide (3b) in

71% isolated yield.

3. Diversification of C-alkylated amides

N

OMe

Me

i. Bu3SnLi, THF, rt

ii. H2O, rtH

O

OHi. SmI2-Et3N-H2O

THF, rt

3a

6 (52%)

7 (75%)

3.1. α-alkylated amide to aldehyde

To a 15 mL clean, oven-dried screw cap reaction tube was added 3a (0.1 mmol) and Bu3SnLi

(320 mol%) in THF under argon atmosphere at 0oC. Then the reaction was stirring at room

temperature for 48 h. After that the reaction mixture was quenched with water and extracted

with dichloromethane (3 x 5 mL). The resultant organic layer was dried over anhydrous

Na2SO4 and the solvent was evaporated under reduced pressure. The crude mixture was

purified by silica gel column chromatography (230-400 mesh size) using petroleum-

ether/ethyl acetate as an eluting system.

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3.2. α-alkylated amide to alcohol

To a 15 mL clean, oven-dried screw cap reaction tube was added 3a (0.1 mmol) and

samarium(II) iodide (THF solution, 8 equiv) followed by Et3N (72 equiv) and H2O (72 equiv)

under argon atmosphere, resulted the formation of a dark brown color of the SmI2-Et3N-H2O

complex. Then the reaction mixture was stirred for 24 h at room temperature. After the

completion of reaction the reaction mixture was diluted with CH2Cl2 and NaOH (1N)

solution. The aqueous layer was extracted with CH2Cl2 (3 x 30 mL) and the combined

organic layers were dried over Na2SO4, and concentrated. The crude mixture was purified by

silica gel column chromatography (230-400 mesh size) using petroleum-ether/ethyl acetate as

an eluting system.

4. Characterization Data of Compounds

N,N-dimethyl-3-phenylpropanamide (3a)

The general procedure was followed to afford the title compound as colourless liquid,

isolated yield: 82%, 72 mg; 1H NMR (200 MHz, CDCl3) δ 7.39-7.33 (m, 2H), 7.31-7.25 (m,

3H), 3.07-2.98 (m, 8H), 2.69 (t, J = 6.7 Hz, 2H); 13C NMR (50 MHz, CDCl3) δ 172.1, 141.4,

128.4, 128.3, 126.0, 37.0, 35.3,35.2, 31.3. HRMS (EI) m/z Calcd for C11H16NO [M+H]+:

178.1226; Found: 178.1233.

N,N-dimethyl-3-(p-tolyl)propanamide (3b)

The general procedure was followed to afford the title compound as colourless oil, isolated

yield: 85%, 81 mg; 1H NMR (200 MHz, CDCl3) δ 7.22-7.03 (m, 4H), 3.04-2.86 (m, 8H), 2.60

(t, J = 6.7 Hz, 2H), 2.33(s, 3H); 13C NMR (50 MHz, CDCl3) δ 172.3, 138.4, 135.5, 129.0,

128.2, 37.1, 35.4 (2), 30.9, 20.9; HRMS (EI) m/z Calcd for C12H18NO [M+H]+: 192.1383;

Found: 192.1384.

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N,N-dimethyl-3-(m-tolyl)propanamide (3c)

The general procedure was followed to afford the title compound as colourless oil, isolated

yield: 78%, 74 mg; 1H NMR (200 MHz, CDCl3) δ = 7.18 (t, J = 8.1 Hz, 1H), 7.04-7.01 (m,

3H), 2.95-2.90 (m, 8H), 2.61 (t, J = 7.3 Hz, 2H), 2.34 (s, 3H); 13C NMR (50 MHz, CDCl3) δ

= 172.2, 141.3, 137.9, 129.1, 128.3, 126.7, 125.3, 37.1, 35.3, 35.3, 31.2, 21.3; HRMS (EI):

m/z Calcd for C12H18NO [M+H]+: 192.1383; Found: 192.1384.

N,N-dimethyl-3-(o-tolyl)propanamide (3d)

The general procedure was followed to afford the title compound as colourless oil, isolated

yield: 70%, 67 mg; 1H NMR (500 MHz, CDCl3) δ 7.20-7.07 (m, 4H), 3.00-2.90 (m, 8H), 2.57

(t, J = 6.7 Hz, 2H), 2.34(s, 3H); 13C NMR (126 MHz, CDCl3) δ 172.3, 139.5, 135.9, 130.2,

128.7, 126.2, 126.0, 37.1, 35.4, 33.8, 28.7, 19.3; HRMS (EI): m/z Calcd for C12H18NO

[M+H]+: 192.1383; Found: 192.1384.

3-(4-methoxyphenyl)-N,N-dimethylpropanamide (3e)

The general procedure was followed to afford the title compound as colourless oil, isolated

yield: 88%, 91 mg; 1H NMR (200 MHz, CDCl3) δ 7.20-7.06 (td, J = 8.6, 2.1 Hz, 2H), 6.89-

6.76 (td, J = 8.6, 2.1 Hz, 2H), 3.78 (s, 3H), 2.98-2.84 (m, 8H), 2.58 (t, J = 6.6 Hz, 2H); 13C

NMR(50 MHz, CDCl3) δ 172.2, 157.8, 133.4, 129.2, 113.7, 55.1, 37.0, 35.4, 35.3, 30.3;

HRMS (EI): m/z Calcd for C12H18NO2[M+H]+: 208.1332; Found: 208.1331.

3-(3-methoxyphenyl)-N,N-dimethylpropanamide (3f)

The general procedure was followed to afford the title compound as colorless oil, isolated

yield: 72%, 74mg; 1H NMR (200 MHz, CDCl3) δ 7.23-7.03 (m, 1H), 6.84-6.58 (m, 3H), 3.71

(s, 3H), 3.04-2.72 (m, 8H), 2.53 (t, J = 6.7 Hz, 2H); 13C NMR (50 MHz, CDCl3) δ 172.3,

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159.6, 143.0, 129.4, 120.7, 114.1, 111.3, 55.1, 37.1, 35.4, 35.1, 31.3; HRMS (EI): m/z Calcd

for C12H18NO2[M+H]+: 208.1332; Found: 208.1331.

N,N-dimethyl-3-(4-(methylthio)phenyl)propanamide (3g)

The general procedure was followed to afford the title compound as colourless sticky liquid,

isolated yield: 78%, 87 mg; 1HNMR (200 MHz, CDCl3) δ = 7.23-7.12 (m, 4H), 2.97-2.89 (m,

8H), 2.59 (t, J = 8.3 Hz, 2H), 2.46 (s, 3H); 13CNMR (50 MHz, CDCl3) δ = 172.2, 138.5,

135.7, 128.9, 127.1, 37.2, 35.5, 35.1, 30.7, 16.2. HRMS(EI): m/z Calcd for C12H17NOS

[M+H]+: 224.1031; Found: 224.1029.

3-(4-chlorophenyl)-N,N-dimethylpropanamide (3h)

The general procedure was followed to afford the title compound as colourless oil, isolated

yield: 65%, 68 mg; 1H NMR (500 MHz, CDCl3) δ 7.38-7.34 (m, 2H), 7.31-7.28 (m, 2H),

3.06-2.97 (m, 8H), 2.69 (t, J = 6.6 Hz, 2H); 13C NMR (126 MHz, CDCl3) δ 172.2, 141.5,

128.5, 128.4, 126.1, 37.2, 35.4, 35.3, 33.4; HRMS (EI): m/z Calcd for C11H15NOCl [M+H]+:

212.0837; Found: 212.0837.

3-(4-fluorophenyl)-N,N-dimethylpropanamide (3i)

The general procedure was followed to afford the title compound as colourless sticky liquid.

Yield: 62%, 60 mg; 1HNMR (500 MHz, CDCl3) δ = 7.19-7.16 (m, 2H), 6.96 (t, J = 8.8 Hz,

2H), 2.96-2.91 (m, 8H), 2.59 (t, J = 8.0 Hz, 2H); 13CNMR (126 MHz, CDCl3) δ = 172.0,

162.3, 160.4, 137.0, 129.7, 128.4, 126.1, 115.2, 115.0, 37.1, 35.4, 35.2, 30.5.

3-(3,4-dimethoxyphenyl)-N,N-dimethylpropanamide (3j)

The general procedure was followed to afford the title compound as a colorless oil, isolated

yield: 80%, 95 mg; 1H NMR (500 MHz, CDCl3) δ 6.81-6.71 (m, 3H), 3.86 (s, 3H), 3.84 (s,

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3H), 2.96-2.84 (m, 8H), 2.59 (t, J = 6.8 Hz, 2H); 13C NMR (126 MHz, CDCl3) δ 172.2,

148.7, 147.2, 134.0, 120.0, 111.7, 111.1, 55.8, 55.7, 37.1, 35.4, 35.3, 30.9; HRMS (EI): m/z

Calcd for C13H20NO3 [M+H]+: 238.1438; Found: 238.1439.

N,N-dimethyl-3-(naphthalen-2-yl)propanamide (3k)

The general procedure was followed to afford the title compound as colourless oil, isolated

yield: 76%, 86 mg; 1H NMR (500 MHz, CDCl3) δ 7.84-7.76 (m, 3H), 7.67 (m, 1H), 7.49-7.41

(m, 2H), 7.40-7.35 (m, 1H), 3.15 (t, J = 8.4 Hz, 2H), 2.97 (s, 3H), 2.94 (s, 3H), 2.71 (t, J =

7.4Hz, 2H); 13C NMR (126 MHz, CDCl3) δ 172.1, 138.9, 133.6, 132.0, 127.9, 127.6, 127.4,

127.2, 126.4, 125.9, 125.2, 37.2, 35.4, 35.2, 31.5; HRMS (EI): m/z Calcd for C15H18NO

[M+H]+: 228.1383; Found: 228.1384.

N,N-dimethyloctanamide (3l)

The general procedure was followed to afford the title compound as colourless oil, isolated

yield: 56%, 48 mg; 1H NMR (200 MHz, CDCl3) δ 2.98 (s, 3H), 2.91 (s, 3H), 2.28 (t, J = 7.1

Hz, 2H), 1.69-1.48 (m, 2H), 1.32-1.19 (m, 8H), 0.89-0.80 (m, 3H); 13C NMR (50 MHz,

CDCl3) δ 173.3, 37.2, 35.2, 33.4, 31.6, 29.4, 29.0, 25.1, 22.5, 13.9; HRMS (EI): m/z Calcd

for C10H22NO [M+H]+: 172.1696; Found: 172.1697.

3-cyclopropyl-N,N-dimethylpropanamide (3m)

The general procedure was followed to afford the title compound as a colorless oil, isolated

yield: 52%, 37 mg; 1H NMR (500 MHz, CDCl3) δ 3.03 (s, 3H), 2.94 (s, 3H), 2.42 (t, J = 7.4

Hz, 2H), 1.52 (q, J = 7.6 Hz, 2H), 0.73 (m, 1H), 0.48-0.34 (m, 2H), 0.10-0.02 (m, 2H); 13C

NMR (126 MHz, CDCl3) δ 173.1, 37.3, 35.3, 33.3, 30.4, 10.7, 4.5; HRMS (EI): m/z Calcd

for C8H16NO [M+H]+: 142.1226; Found: 142.1228.

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3-(furan-2-yl)-N,N-dimethylpropanamide (3n)

The general procedure was followed to afford the title compound as colourless oil, isolated

yield: 75%, 62 mg; 1H NMR (500 MHz, CDCl3) δ 7.31 (m, 1H), 6.30-6.25 (m, 1H), 6.06-6.00

(m, 1H), 3.02-2.94 (m, 8H), 2.66 (t, J = 8.7 Hz, 2H); 13C NMR (126 MHz, CDCl3) δ 171.8,

154.9, 140.9, 110.2, 105.2, 37.1, 35.4, 31.8, 23.7; HRMS (EI): m/z Calcd for C9H14O2N

[M+H]+: 168.1019; Found: 168.1027.

1-(pyrrolidin-1-yl)-3-(p-tolyl)propan-1-one (4a)

The general procedure was followed to afford the title compound as colourless oil, isolated

yield: 65%, 70 mg; 1H NMR (500 MHz, CDCl3) δ 7.11 (s, 4H), 3.67-3.57 (m, 4H), 3.52 (t, J

= 5.0 Hz, 2H), 3.36 (t, J = 4.4 Hz, 2H), 2.94 (t, J = 8.2 Hz, 2H), 2.60 (t, J = 7.6 Hz, 2H), 2.32

(s, 3H); 13C NMR (126 MHz, CDCl3) δ 170.9, 137.9, 135.7, 129.2, 128.3, 66.8, 66.4, 45.9,

41.9, 34.9, 30.9, 20.9; HRMS (EI): m/z Calcd for C14H20NO [M+H]+: 218.1539; Found:

218.1545.

1-(piperidin-1-yl)-3-(p-tolyl)propan-1-one (4b)

The general procedure was followed to afford the title compound as colourless oil, isolated

yield: 74%, 85 mg; 1H NMR (500 MHz, CDCl3) δ 7.16-7.06 (m, 4H), 3.56 (t, J = 6.7 Hz,

2H), 3.35 (t, J = 5.7 Hz, 2H), 2.93 (t, J = 8.3 Hz, 2H), 2.60 (t, J = 7.7 Hz, 2H), 2.32 (s, 3H),

1.65-1.58 (m, 2H), 1.56-1.45 (m, 4H); 13C NMR (126 MHz, CDCl3) δ 170.5, 138.4, 135.5,

129.1, 128.3, 46.6, 42.7, 35.4, 31.1, 26.4, 25.5, 24.5, 20.9; HRMS (EI): m/z Calcd for

C15H22NO [M+H]+: 232.1696; Found: 232.1697.

1-morpholino-3-(p-tolyl)propan-1-one (4c)

The general procedure was followed to afford the title compound as colourless oil, isolated

yield: 54%, 69 mg; 1H NMR (500 MHz, CDCl3) δ 7.13-7.09 (m, 4H), 3.47 (t, J = 6.7 Hz,

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S14

2H), 3.30 (t, J = 6.9 Hz, 2H), 2.95 (t, J = 8.5 Hz, 2H), 2.54 (t, J = 8.5 Hz, 2H), 2.32 (s, 3H),

1.89 (m, 2H), 1.82 (m, 2H); 13C NMR (126 MHz, CDCl3) δ 170.9, 138.4, 135.5, 129.0, 128.3,

46.5, 45.6, 36.9, 30.7, 26.0, 24.3, 20.9. HRMS (EI): m/z Calcd for C14H19NO2Na [M+Na]+:

256.1308; Found:256.1306.

N-methyl-N-phenyl-3-p-tolylpropanamide (4d)

The general procedure was followed to afford the title compound as colourless oil, isolated

yield: 72%, 91 mg; 1HNMR (200 MHz, CDCl3) δ = 7.38-7.33 (m, 3H), 7.07-6.94 (m, 5H),

3.26 (s, 3H), 2.88 (t, J = 8.2 Hz, 2H), 2.36 (t, J = 7.9 Hz, 2H), 2.30 (s, 3H). 13CNMR (50

MHz, CDCl3) δ = 172.3, 143.9, 138.1, 135.4, 129.7, 128.9, 128.2, 127.7, 127.3, 37.3, 36.1,

31.3, 20.9. HRMS(EI): m/z Calcd for C17H19NO [M+H]+: 254.1467; Found: 254.1466.

1-methyl-3-(4-methylbenzyl)piperidin-2-one (4e)

The general procedure was followed to afford the title compound as colourless oil, isolated

yield: 48%, 52mg; 1H NMR (500 MHz, CDCl3) δ 7.15-7.04 (m, 4H), 3.49-3.33 (m, 1H),

3.31-3.13 (m, 2H), 2.95 (s, 3H), 2.68-2.45 (m, 2H), 2.31(s, 3H), 1.90-1.57 (m, 3H), 1.53-1.36

(m, 1H); 13C NMR (126 MHz, CDCl3) δ 172.0, 137.0, 135.4, 129.0, 128.9, 50.1, 43.3, 37.3,

34.9, 25.7, 21.3, 20.9; HRMS (EI): m/z Calcd for C14H20NO [M+H]+: 218.1539; Found:

218.1545.

3-(4-methylbenzyl)piperidin-2-one (4f)

The general procedure was followed to afford the title compound as colourless oil. Here we

got N-alkylation product rather than C-alkylation product. Isolated yield: 35%, 36 mg; 1H

NMR (200 MHz, CDCl3) δ = 7.18-7.09 (m, 4H), 4.56 (s, 2H), 3.18 (t, J = 4.4 Hz, 2H), 2.46

(t, J = 6.3 Hz, 2H), 2.33 (s, 3H), 1.78-1.75 (m, 4H); 13C NMR (50 MHz, CDCl3) δ = 169.7,

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S15

136.9, 134.2, 129.2, 128.0, 49.7, 47.0, 32.3, 23.1, 21.3, 21.0; HRMS (EI): m/z Calcd for

C13H18NO [M+H]+: 204.1383; Found: 204.1386.

tert-butyl 3-(4-methoxyphenyl)propanoate (5a)

The general procedure was followed to afford the title compound as colorless sticky liquid.

Isolated yield: 72%, 85 mg; 1HNMR (200 MHz, CDCl3) δ = 7.13 (d, J = 8.5 Hz, 2H), 6.83 (d,

J = 8.7 Hz, 2H), 3.79 (s, 3H), 2.86 (t, J = 8.1 Hz, 2H), 2.51 (t, J = 7.3 Hz, 2H), 1.43 (s, 9H);

13CNMR (50 MHz, CDCl3) δ = 172.4, 157.9, 132.8, 129.2, 113.8, 80.2, 55.2, 37.4, 30.2, 28.1.

(Known compound: Deibl, N.; Kempe, R. J. Am. Chem. Soc. 2016, 138, 10786-10789).

tert-butyl 3-p-tolylpropanoate (5b)

The general procedure was followed to afford the title compound as colorless sticky liquid.

Isolated yield: 65%, 71 mg; 1HNMR (400 MHz, CDCl3) δ = 7.12-7.10 (m, 4H), 2.90 (t, J =

7.9 Hz, 2H), 2.54 (t, J = 7.9 Hz, 2H), 2.34 (s, 3H), 1.45 (s, 9H); 13CNMR (100 MHz, CDCl3)

δ = 172.3, 137.7, 135.5, 129.0, 128.1, 80.2, 37.2, 30.7, 28.0, 20.9. (Known compound: Deibl,

N.; Kempe, R. J. Am. Chem. Soc. 2016, 138, 10786-10789).

tert-butyl 3-o-tolylpropanoate (5c)

The general procedure was followed to afford the title compound as colorless sticky liquid.

Isolated yield: 54%, 59 mg; 1HNMR (400 MHz, CDCl3) δ = 7.16-7.14 (m, 4H), 2.91 (t, J =

7.9 Hz, 2H), 2.51 (t, J = 8.5 Hz, 2H), 2.34 (s, 3H), 1.45 (s, 9H); 13CNMR (100 MHz, CDCl3)

δ = 172.4, 138.9, 135.9, 130.2, 128.5, 126.2, 125.9, 80.3, 35.7, 28.4, 28.1, 19.3. (Known

compound: Deibl, N.; Kempe, R. J. Am. Chem. Soc. 2016, 138, 10786-10789).

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S16

3-phenylpropanal (6)

Colourless liquid, 35 mg, 52% yield; 1H NMR (500 MHz, CDCl3) δ 9.89 (s, 1H), 7.41-7.33

(m, 2H), 7.30-7.24 (m, 3H), 3.04 (t, J = 6.4 Hz, 2H), 2.85 (t, J = 7.4 Hz, 2H); 13C NMR (126

MHz, CDCl3) δ 200.8, 139.5, 127.8, 127.5, 125.5, 44.5, 27.3; HRMS (EI) m/z Calcd for

C9H10ONa [M+Na]+: 157.0624; Found: 157.0626.

3-phenylpropan-1-ol (7)

Colouless liquid, 51 mg, 75% yield; 1H NMR (500 MHz, CDCl3) δ 7.42-7.34 (m, 2H), 7.33-

7.22 (m, 3H), 3.73 (t, J = 6.4 Hz, 2H), 2.79 (t, J = 7.4 Hz, 2H), 2.42 (brs, 1H), 1.97 (p, J = 6.7

Hz, 2H); 13C NMR (126 MHz, CDCl3) δ 141.7, 128.3, 128.2, 125.7, 61.9, 34.1, 31.9; HRMS

(EI) m/z Calcd for C9H12ONa [M+Na]+: 159.0780; Found: 159.0783.

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S17

5. Copy of 1H & 13C NMR

10 9 8 7 6 5 4 3 2 1 0Chemical Shift (ppm)

2.028.012.972.04

7.38

7.36

7.34

7.30

7.29

7.27

3.06

3.04

3.02

2.99

2.70

2.69

2.67

1H-NMR of 3a

180 160 140 120 100 80 60 40 20 0Chemical Shift (ppm)

172.

09

141.

37

128.

3112

5.97

77.2

677

.00

76.7

4

37.0

435

.31

35.1

931

.26

13C-NMR of 3a

N

OMe

Me

N

OMe

Me

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S18

10 9 8 7 6 5 4 3 2 1 0Chemical Shift (ppm)

3.062.108.004.01

7.12

2.98

2.98

2.96

2.94

2.90

2.64

2.61

2.60

2.56

2.33

1H-NMR of 3b

180 160 140 120 100 80 60 40 20 0Chemical Shift (ppm)

172.

26

138.

3613

5.53

129.

0912

8.25

77.6

377

.00

76.3

7

37.1

235

.45

35.3

830

.88

20.9

6

13C-NMR of 3b

Me

N

OMe

Me

Me

N

OMe

Me

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S19

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)

3.002.087.652.840.97

7.23

7.18

7.15

7.04

7.01

2.96

2.94

2.90

2.65

2.61

2.57

2.34

1H-NMR of 3c

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0Chemical Shift (ppm)

172.

25

141.

3213

7.93

129.

1312

8.28

126.

7412

5.30

77.6

377

.00

76.3

6

37.0

935

.28

31.2

2

21.2

9

13C-NMR of 3c

N

O

N

O

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S20

9 8 7 6 5 4 3 2 1 0Chemical Shift (ppm)

3.072.008.063.99

7.27

7.17

7.16

7.15

7.14

7.13

2.99

2.97

2.95

2.94

2.59

2.57

2.56

2.34

1H-NMR of 3d

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0Chemical Shift (ppm)

172.

29

139.

5413

5.95

130.

2412

8.74

126.

2312

6.06

77.2

577

.00

76.7

4

37.1

035

.40

33.8

9

28.6

7

19.2

5

13C-NMR of 3d

N

OMe

Me

Me

N

OMe

Me

Me

Page 21: Supporting Information: Ester with Alcohols via …S1 Supporting Information: Manganese-Catalyzed Direct C-C Coupling of α-C−H bonds of Amides and Ester with Alcohols via Hydrogen

S21

10 9 8 7 6 5 4 3 2 1 0Chemical Shift (ppm)

2.007.953.002.001.98

7.17

7.16

7.13

7.12

6.85

6.84

6.82

6.81

3.78

2.94

2.93

2.91

2.91

2.90

2.87

2.62

2.58

2.54

1H-NMR of 3e

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0Chemical Shift (ppm)

172.

16

157.

83

133.

3812

9.21

113.

72

77.6

477

.00

76.3

7

55.1

1

37.0

435

.39

35.2

630

.35

13C-NMR of 3e

N

OMe

MeMeO

N

OMe

MeMeO

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S22

10 9 8 7 6 5 4 3 2 1 0Chemical Shift (ppm)

1.968.063.003.121.15

7.17

7.13

7.09

6.75

6.72

6.69

6.65

6.64

3.71

2.88

2.86

2.82

2.57

2.53

2.50

1H-NMR of 3f

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0Chemical Shift (ppm)

172.

26

159.

61

142.

97

129.

35

120.

67

114.

0811

1.32

77.6

377

.00

76.3

6

55.0

5

37.1

235

.40

35.0

931

.34

13C-NMR of 3f

N

OMe

Me

OMe

N

OMe

Me

OMe

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S23

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)

3.422.168.004.36

7.23

7.18

7.17

7.12

2.97

2.95

2.93

2.89

2.63

2.59

2.56

2.46

1H-NMR of 3g

180 160 140 120 100 80 60 40 20 0Chemical Shift (ppm)

172.

20

138.

5013

5.69

128.

9512

7.14

77.6

377

.00

76.3

6

37.1

735

.46

35.1

430

.75

16.2

3

13C-NMR of 3g

N

O

MeS

N

O

MeS

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S24

9 8 7 6 5 4 3 2 1 0Chemical Shift (ppm)

2.008.362.222.00

7.37

7.36

7.34

7.30

7.29

7.27

3.06

3.04

3.02

3.00

2.70

2.69

2.67

1H-NMR of 3h

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0Chemical Shift (ppm)

172.

23

141.

51

128.

4712

6.10

77.3

077

.04

76.7

9

37.1

735

.45

35.3

231

.39

13C-NMR of 3h

N

OMe

MeCl

N

OMe

MeCl

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S25

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)

1.978.401.862.00

7.27

7.19

7.18

7.17

7.16

6.98

6.96

6.95

2.96

2.95

2.95

2.93

2.91

2.61

2.59

2.58

1H-NMR of 3i

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0Chemical Shift (ppm)

172.

01

162.

3416

0.40

137.

05

129.

7512

8.42

128.

3812

6.05

115.

2111

5.04

77.2

577

.00

76.7

4

37.1

235

.43

35.1

930

.46

13C-NMR of 3i

N

O

F

N

O

F

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S26

10 9 8 7 6 5 4 3 2 1 0Chemical Shift (ppm)

2.108.323.053.002.99

6.79

6.77

6.75

6.75

3.86

3.84

2.94

2.92

2.90

2.89

2.60

2.59

2.57

1H-NMR of 3j

180 160 140 120 100 80 60 40 20 0Chemical Shift (ppm)

172.

17

148.

7314

7.25

134.

03

120.

07

111.

7011

1.14

77.2

677

.00

76.7

4

55.8

155

.74

37.1

235

.45

35.3

430

.95

13C-NMR of 3j

N

OMe

MeMeO

OMe

N

OMe

MeMeO

OMe

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S27

8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)

2.003.052.952.070.961.950.993.00

7.82

7.81

7.79

7.78

7.67

7.46

7.45

7.44

7.39

7.37

7.27

3.16

3.15

3.13

2.97

2.94

2.73

2.71

2.70

1H-NMR of 3k

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0Chemical Shift (ppm)

172.

12

138.

9813

3.58

132.

0512

7.98

127.

5712

7.41

127.

1812

6.44

125.

9412

5.24

77.2

677

.00

76.7

5

37.1

535

.43

35.1

731

.48

13C-NMR of 3k

N

OMe

Me

N

OMe

Me

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S28

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)

3.078.072.182.002.863.04

7.27

2.98

2.91

2.31

2.28

2.24

1.63

1.59

1.59

1.29

1.28

1.26

1.25

1.25

1.24

0.88

0.87

0.85

0.81

1H-NMR of 3l

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0Chemical Shift (ppm)

173.

33

77.6

477

.00

76.3

7

37.2

335

.25

33.3

531

.64

29.3

929

.04

25.1

222

.54

13.9

9

13C-NMR of 3l

N

OMe

Me

N

OMe

Me

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S29

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)

1.992.111.072.212.003.022.91

7.27

7.27

3.03

2.94

2.46

2.42

2.38

1.58

1.55

1.51

1.47

0.77

0.73

0.45

0.44

0.44

0.41

0.40

0.07

0.06

0.06

1H-NMR of 3m

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0Chemical Shift (ppm)

173.

08

77.2

576

.99

76.7

4

37.2

935

.32

33.3

430

.36

10.6

8

4.46

13C-NMR of 3m

N

OMe

Me

N

OMe

Me

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S30

8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)

2.138.411.001.001.01

7.31

7.27

6.29

6.28

6.28

6.03

6.03

6.03

3.01

2.99

2.98

2.96

2.67

2.66

2.64

1H-NMR of 3n

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0Chemical Shift (ppm)

171.

78

154.

97

140.

97

110.

22

105.

23

77.2

577

.00

76.7

4

37.0

935

.45

31.7

9

23.6

9

13C-NMR of 3n

N

OMe

MeO

N

OMe

MeO

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S31

8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)

3.002.011.991.961.993.973.89

7.27

7.11

3.64

3.63

3.63

3.62

3.52

3.52

3.37

3.36

2.96

2.94

2.93

2.61

2.60

2.58

2.32

1H-NMR of 4a

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0Chemical Shift (ppm)

170.

93

137.

9013

5.73

129.

1612

8.28

77.2

677

.00

76.7

5

66.8

266

.42

45.9

241

.88

34.9

330

.99

20.9

6

13C-NMR of 4a

N

O

N

O

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S32

8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)

4.022.293.011.972.002.022.083.90

7.27

7.13

7.12

7.11

7.09

3.58

3.56

3.55

3.36

3.35

3.33

2.95

2.93

2.91

2.62

2.60

2.59

2.32

1.62

1.61

1.54

1.53

1.49

1.49

1.48

1H-NMR of 4b

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0Chemical Shift (ppm)

170.

50

138.

3713

5.53

129.

1112

8.26

77.2

677

.00

76.7

5

46.5

842

.67

35.3

631

.13

26.3

725

.52

24.5

220

.97

13C-NMR of 4b

N

O

N

O

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S33

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)

2.292.153.001.992.012.011.983.88

7.13

7.12

7.10

7.09

3.48

3.47

3.45

3.31

3.30

3.29

2.96

2.95

2.93

2.56

2.54

2.53

2.32

1.90

1.89

1.88

1.84

1.82

1H-NMR of 4c

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0Chemical Shift (ppm)

170.

86

138.

3713

5.48

129.

0512

8.26

77.2

577

.00

76.7

4

46.5

145

.59

36.8

8

30.7

026

.01

24.3

320

.94

13C-NMR of 4c

N

O

O

N

O

O

Page 34: Supporting Information: Ester with Alcohols via …S1 Supporting Information: Manganese-Catalyzed Direct C-C Coupling of α-C−H bonds of Amides and Ester with Alcohols via Hydrogen

S34

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)

3.112.112.023.005.932.92

7.38

7.37

7.36

7.34

7.33

7.27

7.07

7.03

6.98

6.94

3.26

2.92

2.88

2.84

2.40

2.36

2.32

2.30

1H NMR of 4d

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0Chemical Shift (ppm)

172.

28

143.

9913

8.13

135.

4212

9.66

128.

9612

8.23

127.

6812

7.25

77.6

477

.00

76.3

7

37.3

136

.13

31.2

6

20.9

2

13C NMR of 4d

N

OPh

N

OPh

Page 35: Supporting Information: Ester with Alcohols via …S1 Supporting Information: Manganese-Catalyzed Direct C-C Coupling of α-C−H bonds of Amides and Ester with Alcohols via Hydrogen

S35

9 8 7 6 5 4 3 2 1 0Chemical Shift (ppm)

1.032.061.053.061.021.003.002.021.034.17

7.27

7.09

7.07

3.41

3.40

3.38

3.38

3.26

3.25

3.24

3.23

2.95

2.61

2.59

2.57

2.31

1.70

1.69

1.45

1.44

1H-NMR of 4e

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0Chemical Shift (ppm)

172.

01

137.

0213

5.43

129.

0312

8.92

77.6

377

.00

76.3

7

50.0

9

43.3

1

37.3

134

.89

25.6

721

.35

20.9

3

13C-NMR of 4e

NMe

O Me

NMe

O Me

Page 36: Supporting Information: Ester with Alcohols via …S1 Supporting Information: Manganese-Catalyzed Direct C-C Coupling of α-C−H bonds of Amides and Ester with Alcohols via Hydrogen

S36

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5Chemical Shift (ppm)

3.923.141.971.981.954.00

7.18

7.14

7.09

4.56

3.21

3.18

3.16

3.15

2.49

2.48

2.46

2.43

2.33

1.78

1.77

1.75

1H-NMR of 4f

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0Chemical Shift (ppm)

169.

74

136.

8713

4.18

129.

1512

8.04

77.6

377

.00

76.3

7

49.7

247

.04

32.3

5

23.1

021

.32

21.0

3

13C-NMR of 4f

N

O

N

O

Page 37: Supporting Information: Ester with Alcohols via …S1 Supporting Information: Manganese-Catalyzed Direct C-C Coupling of α-C−H bonds of Amides and Ester with Alcohols via Hydrogen

S37

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)

9.021.991.983.001.971.95

7.27

7.15

7.10

6.85

6.84

6.82

6.81

3.79

2.90

2.86

2.82

2.55

2.51

2.47

1.43

1H-NMR of 5a

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0Chemical Shift (ppm)

172.

35

157.

93

132.

8412

9.22

113.

76

80.2

477

.63

77.0

076

.37

55.2

1

37.3

6

30.2

428

.05

13C-NMR of 5a

O

OtBu

OMe

O

OtBu

OMe

Page 38: Supporting Information: Ester with Alcohols via …S1 Supporting Information: Manganese-Catalyzed Direct C-C Coupling of α-C−H bonds of Amides and Ester with Alcohols via Hydrogen

S38

7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)

8.853.091.961.984.00

7.11

7.10

2.91

2.90

2.88

2.56

2.54

2.52

2.34

1.45

1H-NMR of 5b

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0Chemical Shift (ppm)

172.

32

137.

6613

5.49

129.

0212

8.40

128.

13

80.2

277

.32

77.0

076

.69

37.1

9

30.6

628

.03

20.9

5

13C-NMR of 5b

O

OtBu

O

OtBu

Page 39: Supporting Information: Ester with Alcohols via …S1 Supporting Information: Manganese-Catalyzed Direct C-C Coupling of α-C−H bonds of Amides and Ester with Alcohols via Hydrogen

S39

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)

8.833.251.952.004.09

7.15

7.15

7.14

2.93

2.91

2.89

2.53

2.52

2.51

2.49

2.34

1.45

1H-NMR of 5c

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0Chemical Shift (ppm)

172.

43

138.

8613

5.97

130.

1712

8.48

126.

2312

5.98

80.3

477

.32

77.0

076

.69

35.7

128

.41

28.0

6

19.2

6

13C-NMR of 5c

O

OtBu

O

OtBu

Page 40: Supporting Information: Ester with Alcohols via …S1 Supporting Information: Manganese-Catalyzed Direct C-C Coupling of α-C−H bonds of Amides and Ester with Alcohols via Hydrogen

S40

11 10 9 8 7 6 5 4 3 2 1 0Chemical Shift (ppm)

2.001.993.032.020.99

9.89

7.38

7.37

7.29

3.04

2.85

1H-NMR of 6

220 200 180 160 140 120 100 80 60 40 20 0 -20Chemical Shift (ppm)

200.

79

139.

54

127.

8112

7.51

125.

51

77.2

577

.00

76.7

4

44.4

8

27.3

2

13C-NMR of 6

H

O

H

O

Page 41: Supporting Information: Ester with Alcohols via …S1 Supporting Information: Manganese-Catalyzed Direct C-C Coupling of α-C−H bonds of Amides and Ester with Alcohols via Hydrogen

S41

9 8 7 6 5 4 3 2 1 0Chemical Shift (ppm)

2.020.972.002.002.881.87

7.39

7.38

7.36

7.30

7.28

7.27

3.75

3.73

3.72

2.80

2.79

2.77

2.42

2.00

1.99

1.97

1.96

1.94

1H-NMR of 7

170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0Chemical Shift (ppm)

141.

75

128.

2712

5.72

77.2

677

.00

76.7

4

61.9

6

34.0

631

.95

13C-NMR of 7

OH

OH

Page 42: Supporting Information: Ester with Alcohols via …S1 Supporting Information: Manganese-Catalyzed Direct C-C Coupling of α-C−H bonds of Amides and Ester with Alcohols via Hydrogen

S42

6. HRMS Data

AM-1 #116 RT: 0.51 AV: 1 NL: 5.36E6T: FTMS + p ESI Full ms [100.00-1500.00]

177.95 178.00 178.05 178.10 178.15 178.20 178.25m/z

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

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178.1233R=70600

C 11 H16 O N = 178.12263.9080 ppm

HRMS Data of 3a

AM-3 #117 RT: 0.52 AV: 1 NL: 6.88E9T: FTMS + p ESI Full ms [100.00-1500.00]

150 160 170 180 190 200 210 220 230 240 250 260m/z

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

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192.1384R=81107

C 12 H18 O N = 192.13830.6336 ppm

214.1208R=77207

C 12 H17 O N Na = 214.12022.8685 ppm

256.1308R=70507

234.1489R=73107

178.1229R=79502

C 11 H16 O N = 178.12261.2524 ppm

219.1571R=73502

241.1391R=68602 248.0752

R=64100152.3460R=62600

162.0868R=72100

HRMS Data of 3b

N

O

3a

N

O

3b

Page 43: Supporting Information: Ester with Alcohols via …S1 Supporting Information: Manganese-Catalyzed Direct C-C Coupling of α-C−H bonds of Amides and Ester with Alcohols via Hydrogen

S43

AM-3 #117 RT: 0.52 AV: 1 NL: 6.88E9T: FTMS + p ESI Full ms [100.00-1500.00]

150 160 170 180 190 200 210 220 230 240 250 260m/z

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

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192.1384R=81107

C 12 H18 O N = 192.13830.6336 ppm

214.1208R=77207

C 12 H17 O N Na = 214.12022.8685 ppm

256.1308R=70507

234.1489R=73107

178.1229R=79502

C 11 H16 O N = 178.12261.2524 ppm

219.1571R=73502

241.1391R=68602 248.0752

R=64100152.3460R=62600

162.0868R=72100

HRMS Data of 3c

AM-3 #117 RT: 0.52 AV: 1 NL: 6.88E9T: FTMS + p ESI Full ms [100.00-1500.00]

150 160 170 180 190 200 210 220 230 240 250 260m/z

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

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192.1384R=81107

C 12 H18 O N = 192.13830.6336 ppm

214.1208R=77207

C 12 H17 O N Na = 214.12022.8685 ppm

256.1308R=70507

234.1489R=73107

178.1229R=79502

C 11 H16 O N = 178.12261.2524 ppm

219.1571R=73502

241.1391R=68602 248.0752

R=64100152.3460R=62600

162.0868R=72100

HRMS Data of 3d

N

O

3c

N

O

3d

Page 44: Supporting Information: Ester with Alcohols via …S1 Supporting Information: Manganese-Catalyzed Direct C-C Coupling of α-C−H bonds of Amides and Ester with Alcohols via Hydrogen

S44

AM-5 #114 RT: 0.51 AV: 1 NL: 4.58E9T: FTMS + p ESI Full ms [100.00-1500.00]

198 200 202 204 206 208 210 212 214 216 218 220 222m/z

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

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208.1331R=78407

C 12 H18 O2 N = 208.1332-0.4945 ppm

209.1358R=77902

206.1178R=77002

C 12 H16 O2 N = 206.11761.3989 ppm

210.1398R=57302

215.0908R=60900

C 11 H14 O2 N Na = 215.0917-4.0442 ppm

HRMS Data of 3e

AM-5 #114 RT: 0.51 AV: 1 NL: 4.58E9T: FTMS + p ESI Full ms [100.00-1500.00]

198 200 202 204 206 208 210 212 214 216 218 220 222m/z

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

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unda

nce

208.1331R=78407

C 12 H18 O2 N = 208.1332-0.4945 ppm

209.1358R=77902

206.1178R=77002

C 12 H16 O2 N = 206.11761.3989 ppm

210.1398R=57302

215.0908R=60900

C 11 H14 O2 N Na = 215.0917-4.0442 ppm

HRMS Data of 3f

N

OMe

MeMeO

3e

N

OMe

Me3f

MeO

Page 45: Supporting Information: Ester with Alcohols via …S1 Supporting Information: Manganese-Catalyzed Direct C-C Coupling of α-C−H bonds of Amides and Ester with Alcohols via Hydrogen

S45

AM-8 #108 RT: 0.48 AV: 1 NL: 2.84E7T: FTMS + p ESI Full ms [100.00-1500.00]

211.75 211.80 211.85 211.90 211.95 212.00 212.05 212.10 212.15m/z

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

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212.0837R=74106

C 11 H15 O N Cl = 212.08370.1231 ppm

212.1046R=70702

HRMS Data of 3h

AM-9 #101 RT: 0.45 AV: 1 NL: 7.13E9T: FTMS + p ESI Full ms [100.00-1500.00]

160 170 180 190 200 210 220 230 240 250 260 270 280 290 300 310 320m/z

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

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238.1439R=72207

C 13 H20 O3 N = 238.14380.6336 ppm

260.1258R=69207

C 13 H19 O3 N Na = 260.12570.4202 ppm

224.1283R=73907

C 12 H18 O3 N = 224.12810.8532 ppm

191.0704R=79707

C 12 H10 N Na = 191.0705-0.5811 ppm

257.1175R=67307

262.1315R=59100

288.1571R=63302

165.0911R=80907

C 10 H13 O2 = 165.09100.8150 ppm

276.0997R=63107

302.1366R=55702

316.1542R=53300

HRMS Data of 3j

N

OMe

MeCl 3h

N

OMe

MeMeO

OMe 3i

Page 46: Supporting Information: Ester with Alcohols via …S1 Supporting Information: Manganese-Catalyzed Direct C-C Coupling of α-C−H bonds of Amides and Ester with Alcohols via Hydrogen

S46

AM-13 #119 RT: 0.53 AV: 1 NL: 6.43E9T: FTMS + p ESI Full ms [100.00-1500.00]

180 190 200 210 220 230 240 250 260 270 280m/z

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

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228.1384R=73707

C 15 H18 O N = 228.13830.2661 ppm

250.1203R=70603

C 15 H17 O N Na = 250.12020.3814 ppm

200.1072R=76407

C 13 H14 O N = 200.10701.1638 ppm

276.1360R=64307

234.1462R=67307

266.0944R=64602

242.1543R=65200

HRMS Data of 3k

AM-6 #122 RT: 0.54 AV: 1 NL: 1.15E10T: FTMS + p ESI Full ms [100.00-1500.00]

120 125 130 135 140 145 150 155 160 165 170 175 180 185 190 195 200 205 210 215m/z

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

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unda

nce

172.1697R=84607

C 10 H22 O N = 172.16960.7705 ppm

194.1517R=79407

C 10 H21 O N Na = 194.15150.9406 ppm

214.1803R=76407

178.1227R=82507

200.1047R=72802

208.0968R=69502

184.1694R=68302

151.0390R=83000

C 9 H6 N Na = 151.0392-1.7166 ppm

130.1229R=89100

C 7 H16 O N = 130.12261.7145 ppm

HRMS Data of 3l

N

OMe

Me

3k

N

OMe

Me3l

Page 47: Supporting Information: Ester with Alcohols via …S1 Supporting Information: Manganese-Catalyzed Direct C-C Coupling of α-C−H bonds of Amides and Ester with Alcohols via Hydrogen

S47

AM-7 #105 RT: 0.47 AV: 1 NL: 3.68E9T: FTMS + p ESI Full ms [100.00-1500.00]

120 130 140 150 160 170 180 190 200 210 220 230m/z

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

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142.1228R=93307

C 8 H16 O N = 142.12260.9255 ppm

164.1047R=87707

C 8 H15 O N Na = 164.10460.7340 ppm

206.1153R=78407

184.1333R=82807130.0865

R=98707224.1282R=73407

194.1541R=79707

168.1384R=84507

214.1200R=69307

154.1228R=85802

HRMS Data of 3m

AM-14 #148 RT: 0.66 AV: 1 NL: 4.93E8T: FTMS + p ESI Full ms [100.00-1500.00]

100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400m/z

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

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unda

nce

168.1027R=87307

C 9 H14 O2 N = 168.10194.8598 ppm

190.0849R=82707

301.1423R=64507214.1212

R=77107 357.1800R=59507

149.0241R=92307

252.0555R=70607

232.0955R=74507 386.2318

R=56807204.1393R=78107

270.0660R=66202 327.1582

R=57807

HRMS Data of 3n

N

OMe

Me3m

N

OMe

MeO3n

Page 48: Supporting Information: Ester with Alcohols via …S1 Supporting Information: Manganese-Catalyzed Direct C-C Coupling of α-C−H bonds of Amides and Ester with Alcohols via Hydrogen

S48

AM-15 #135 RT: 0.60 AV: 1 NL: 9.84E9T: FTMS + p ESI Full ms [100.00-1500.00]

100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 460m/z

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

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218.1545R=76707

C 14 H20 O N = 218.15392.7513 ppm

240.1364R=72907

457.2836R=52807

435.3017R=53607

360.1941R=58307

310.1344R=62407

136.0761R=92907

C 8 H10 O N = 136.07573.0890 ppm

256.1103R=68007

402.2052R=34800

HRMS Data of 4a

AM-12 #124 RT: 0.55 AV: 1 NL: 1.02E10T: FTMS + p ESI Full ms [100.00-1500.00]

170 180 190 200 210 220 230 240 250 260 270 280 290m/z

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

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232.1697R=73107

C 15 H22 O N = 232.16960.6371 ppm

254.1515R=70507

C 15 H21 O N Na = 254.1515-0.0020 ppm

172.1696R=84607

C 10 H22 O N = 172.16960.3273 ppm

234.1755R=70002

256.1579R=64402

251.1431R=68007

270.1252R=64607

290.1514R=58607

214.1805R=65100

197.1651R=62800

226.9516R=63500

HRMS Data of 4b

N

O

Me4a

N

O

Me4b

Page 49: Supporting Information: Ester with Alcohols via …S1 Supporting Information: Manganese-Catalyzed Direct C-C Coupling of α-C−H bonds of Amides and Ester with Alcohols via Hydrogen

S49

AS-31 #263 RT: 1.17 AV: 1 NL: 2.16E6T: FTMS + p ESI Full ms [100.0000-1500.0000]

254.0 254.2 254.4 254.6 254.8 255.0 255.2 255.4 255.6 255.8 256.0 256.2 256.4 256.6 256.8 257.0 257.2m/z

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

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100

Rel

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256.1306R=66107

C 14 H19 O2 N Na = 256.1308-0.7216 ppm

254.1143R=63702

C 14 H17 O2 N Na = 254.1152-3.1507 ppm

257.1077R=60500

255.0934R=59600

HRMS Data of 4c

AM-15 #135 RT: 0.60 AV: 1 NL: 9.84E9T: FTMS + p ESI Full ms [100.00-1500.00]

100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 460m/z

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

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ance

218.1545R=76707

C 14 H20 O N = 218.15392.7513 ppm

240.1364R=72907

457.2836R=52807

435.3017R=53607

360.1941R=58307

310.1344R=62407

136.0761R=92907

C 8 H10 O N = 136.07573.0890 ppm

256.1103R=68007

402.2052R=34800

HRMS Data of 4e

N

O

OMe

4c

NMe

O Me

4e

Page 50: Supporting Information: Ester with Alcohols via …S1 Supporting Information: Manganese-Catalyzed Direct C-C Coupling of α-C−H bonds of Amides and Ester with Alcohols via Hydrogen

S50

AM-23 #107 RT: 0.48 AV: 1 NL: 6.60E9T: FTMS + p ESI Full ms [100.00-1500.00]

160 180 200 220 240 260 280 300 320 340 360 380m/z

0

5

10

15

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204.1386R=79107

C 13 H18 O N = 204.13831.5681 ppm

226.1206R=75103

C 13 H17 O N Na = 226.12021.7040 ppm

242.1154R=72607 323.6699

R=60407272.1261R=67607

288.0911R=61902

174.1282R=72600

C 12 H16 N = 174.12772.5714 ppm

340.6730R=51400

356.0792R=37300

307.1786R=45200

HRMS Data of 4f

AM-21 #100 RT: 0.45 AV: 1 NL: 5.85E6T: FTMS + p ESI Full ms [100.00-1500.00]

155.6 155.8 156.0 156.2 156.4 156.6 156.8 157.0 157.2 157.4 157.6 157.8 158.0m/z

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157.0626R=88802

C 9 H10 O Na = 157.06241.2103 ppm

158.0966R=86902

HRMS Data of 6

N

Me4fO

H

O

6

Page 51: Supporting Information: Ester with Alcohols via …S1 Supporting Information: Manganese-Catalyzed Direct C-C Coupling of α-C−H bonds of Amides and Ester with Alcohols via Hydrogen

S51

AM-20 #107 RT: 0.48 AV: 1 NL: 8.85E7T: FTMS + p ESI Full ms [100.00-1500.00]

148 150 152 154 156 158 160 162 164 166 168 170 172 174m/z

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159.0783R=90007

C 9 H12 O Na = 159.07801.5170 ppm

173.0576R=85107

149.0236R=90602 151.0756

R=90207156.0811R=84707

153.1276R=85202

167.0947R=80802

163.0756R=74900

171.1495R=71600

150.0269R=81300

158.0968R=85400

169.0832R=54800

HRMS Data of 7

OH

7