csj catalogue vol2 press02 · 2015. 8. 10. · Compounds in Catalytic Asymmetric ......
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− 4 − CSJ Journal Selects Vol. 2 Asymmetric Catalysis Use of In Situ Generated Nitrosocarbonyl Compounds in Catalytic Asymmetric α-Hydroxylation and α-Amination Reactions Biplab Maji* and Hisashi Yamamoto* Bull. Chem. Soc. Jpn. 2015, 88, 753-762 doi:10.1246/bcsj.20150040 H. Yamamoto MnO2 PG H N OH * Mg-cat. R 1 O R 2 XR O R 1 O XR O O NHBoc Cu-cat. X = O, S R 2 R 1 O P(OEt)2 O R 1 R 2 O P(OEt)2 NHPG O O * R 2 Cu-cat. R 1 O R 2 O OR R 1 O R 2 O OR N OH PG * secondary amine-cat. O R R OH N OH PG Asymmetric hydroxylation Asymmetric amination nitrosocarbonyl compounds PG N O * Accounts for C-X Bond Formation Nitrosocarbonyl as Electrophilic N/O Source; Cu, Mg Catalysts Chiral Ammonium Hypoiodite-catalyzed Enantioselective Oxidative Dearomatization of 1-Naphthols Using Hydrogen Peroxide Muhammet Uyanik, Niiha Sasakura, Erina Kaneko, Kento Ohori, and Kazuaki Ishihara* Chem. Lett. 2015, 44, 179-181 doi:10.1246/cl.141012 K. Ishihara OH OH O O O O chiral precatalyst 30% H 2 O 2 Toluene/H 2 O, 20 °C N + I – Ar Ar R R high yield, high ee Ar = 3,5-[3,5-(CF 3 ) 2 C 6 H 3 ] 2 C 6 H 3 Editor's Choice Oxidative Dearomatization; Chiral Hypoiodite 1,4-Addition Reaction of 5H-Oxazol-4-ones to Allenic Esters and Ketones Catalyzed by Chiral Guanidines Nari Jin, Tomonori Misaki,* and Takashi Sugimura* Chem. Lett. 2013, 42, 894-896 doi:10.1246/cl.130295 T. Misaki O N O R 1 + 1a (5 mol%) N N N H OH F3C CF3 CF 3 CF3 O N O R 1 R 2 O chiral γ -butenolide 1a R 2 O Cl Cl up to 98 % ee Me Me R 2 = OPh or alkyl OMe O O O R 1 (R 2 = OPh) OH O O O (+)-crobarbatic acid 2 3 4 6 4 8 Editor's Choice Enantioselective 1,4-Addition; Organocatalysts Enantioselective Synthesis Induced by the Helical Molecular Arrangement in the Chiral Crystal of Achiral Tris(2-hydroxyethyl) 1,3,5-Benzenetricarboxylate in Conjunction with Asymmetric Autocatalysis Tsuneomi Kawasaki,* Mizuki Uchida, Yoshiyasu Kaimori, Taisuke Sasagawa, Arimasa Matsumoto, and Kenso Soai* Chem. Lett. 2013, 42, 711-713 doi:10.1246/cl.130185 K. Soai Left-handed M-crystal CD(–)224 KBr N N R 2 OH S CO 2 R 1 R 1 O 2 C CO 2 R 1 R 1 = -CH 2 CH 2 OH Right-handed P-crystal CD(+)224 KBr N N R 2 CHO + i -Pr 2 Zn Asymmetric Autocatalysis N N R 2 OH R Asymmetric Autocatalysis R 2 = t -Bu-C≡C- > 99.5% ee > 99.5% ee Editor's Choice Asymmetric Autocatalysis; Chiral Crystals
Transcript of csj catalogue vol2 press02 · 2015. 8. 10. · Compounds in Catalytic Asymmetric ......
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− 4 −CSJ Journal Selects Vol. 2
Asymmetric Catalysis
Use of In Situ Generated Nitrosocarbonyl Compounds in Catalytic Asymmetric α-Hydroxylation and α-Amination Reactions
Biplab Maji* and Hisashi Yamamoto*Bull. Chem. Soc. Jpn. 2015, 88, 753-762
doi:10.1246/bcsj.20150040
H. Yamamoto
MnO2
PG
HN
OH*
Mg-cat.
R1
O
R2XR
O
R1
O
XR
O
ONHBoc
Cu-cat.X = O, SR
2
R1
OP(OEt)2
O
R1
R2
OP(OEt)2
NHPG
OO
*
R2 Cu-cat.
R1
O
R2
O
OR
R1
O
R2
O
ORN OHPG
*
secondaryamine-cat.
OR R
OHN
OHPG
Asymmetric hydroxylation Asymmetric amination
nitrosocarbonylcompounds
PGN
O
*
Accounts for C-X Bond Formation Nitrosocarbonyl as Electrophilic N/O Source; Cu, Mg Catalysts
Chiral Ammonium Hypoiodite-catalyzed Enantioselective Oxidative Dearomatization of 1-Naphthols Using Hydrogen Peroxide
Muhammet Uyanik, Niiha Sasakura, Erina Kaneko, Kento Ohori, and Kazuaki Ishihara*Chem. Lett. 2015, 44, 179-181
doi:10.1246/cl.141012
K. IshiharaOH
OH
OO
OO
chiral precatalyst30% H2O2
Toluene/H2O, 20 °C
N+
I–Ar
Ar
R Rhigh yield, high ee
Ar = 3,5-[3,5-(CF3)2C6H3]2C6H3
Editor's Choice Oxidative Dearomatization; Chiral Hypoiodite
1,4-Addition Reaction of 5H-Oxazol-4-ones to Allenic Esters and Ketones Catalyzed by Chiral Guanidines
Nari Jin, Tomonori Misaki,* andTakashi Sugimura*Chem. Lett. 2013, 42, 894-896
doi:10.1246/cl.130295
T. Misaki
ON
O
R1
+
1a(5 mol%)
N
N
NH OH
F3C CF3
CF3
CF3
ON
OR1
R2
O
chiral γ -butenolide
1a
R2
O
Cl Clup to 98 % ee
Me
MeR2 = OPh or alkyl
OMe
O
OO
R1
(R2 = OPh)
OH
O
OO
(+)-crobarbatic acid
2
3 4
6
4
8
Editor's Choice Enantioselective 1,4-Addition; Organocatalysts
Enantioselective Synthesis Induced by the Helical Molecular Arrangement in the Chiral Crystal of Achiral Tris(2-hydroxyethyl) 1,3,5-Benzenetricarboxylate in Conjunction with Asymmetric Autocatalysis
Tsuneomi Kawasaki,* Mizuki Uchida,Yoshiyasu Kaimori, Taisuke Sasagawa,Arimasa Matsumoto, and Kenso Soai*Chem. Lett. 2013, 42, 711-713
doi:10.1246/cl.130185
K. Soai
Left−handed M−crystal
CD(–)224KBr
N
NR2
OHS
CO2R1
R1O2C CO2R1
R1 = −CH2CH2OH
Right−handed P−crystal
CD(+)224KBr N
NR2 CHO + i −Pr2Zn
AsymmetricAutocatalysis
N
NR2
OHR
AsymmetricAutocatalysis
R2 = t−Bu−C≡C−
> 99.5% ee
> 99.5% ee
Editor's Choice Asymmetric Autocatalysis; Chiral Crystals
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− 5 − CSJ Journal Selects Vol. 2
Preparation of Diastereomerically Pure and Mixed (S)-PhGly/BIPHEP/Ru(II) Complexes and Their Catalytic Behavior with Li2CO3 in Asymmetric Cyanosilylation of Benzaldehyde
Nobuhito Kurono, Taiki Katayama, and Takeshi Ohkuma*Bull. Chem. Soc. Jpn. 2013, 86, 577-582
doi:10.1246/bcsj.20120351
T. Ohkuma
Selected Paper Asymmetric Cyanosilylation; Ru(II)/BIPHEP Complexes
Asymmetric Synthesis of 1,3-Oxazolidines via Intramolecular Aza-Michael Addition by Bifunctional Organocatalysts
Yukihiro Fukata, Keisuke Asano,* and Seijiro Matsubara*Chem. Lett. 2013, 42, 355-357
doi:10.1246/cl.121245
K. Asano
up to 87% ee(after recrystallization: 98% ee)
R
OO
N
toluene, 0 °C, 24 h
Ts R'
N
NH
NS NH
H
H
CF3 CF3R
OOH
R' H
N
+Ts
Letter Organocatalysts; 1,3-Oxazolidines
Extraordinary Microwave Effect on atropo-Enantioselective Catalytic Reduction of Biaryl Lactones
Kazuya Nushiro, Satoshi Kikuchi, andTohru Yamada*Chem. Lett. 2013, 42, 165-167
doi:10.1246/cl.2013.165
T. Yamada
O
CH3
O
OH3C
CH3
O
CH3
OHM MP
H3CH3C
NB
O
H PhPh
CH3
10 mol%
in THF 30 °C
Microwave2.45 GHz
Microwaveenhancement
Dynamic Kinetic Resolution
Reaction Acceleration
BH3•THF
86% yield, 92% eeConventional:
Microwave:82% yield, 91% ee
/ 4320 min
/ 20 minKeeping high enantioselectivity!!
OH
Editor's Choice Microwave Effect; Catalytic atropo-Enantioselective Reduction
