Direct Catalytic Asymmetric Addition of Acetonitrile to Aldimines

Akira Saito; Naoya Kumagai; Masakatsu Shibasaki

doi:10.1021/acs.orglett.9b02821

Direct Catalytic Asymmetric Addition of Acetonitrile to Aldimines

Akira Saito, Naoya Kumagai, Masakatsu Shibasaki

Research output: Contribution to journal › Article › peer-review

3 Citations (Scopus)

Abstract

Despite significant advances in catalytic asymmetric reactions with decent stereocontrol, those using acetonitrile as a pronucleophile are often disregarded due to their low reactivity and insufficient enantioselectivity. Herein we report the resurgence of this reaction in the chemical toolbox with high enantioselectivity (avg. > 95% ee). The combined use of a Ni(II) complex ligated with a chiral biscarbene and ^tBuOK engages acetonitrile in the catalytic generation of an α-cyanocarbanion and subsequent highly enantioselective addition to aldimines.

Original language	English
Pages (from-to)	8187-8190
Number of pages	4
Journal	Organic Letters
Volume	21
Issue number	20
DOIs	https://doi.org/10.1021/acs.orglett.9b02821
Publication status	Published - 2019 Oct 18
Externally published	Yes

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry

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10.1021/acs.orglett.9b02821

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title = "Direct Catalytic Asymmetric Addition of Acetonitrile to Aldimines",

abstract = "Despite significant advances in catalytic asymmetric reactions with decent stereocontrol, those using acetonitrile as a pronucleophile are often disregarded due to their low reactivity and insufficient enantioselectivity. Herein we report the resurgence of this reaction in the chemical toolbox with high enantioselectivity (avg. > 95% ee). The combined use of a Ni(II) complex ligated with a chiral biscarbene and tBuOK engages acetonitrile in the catalytic generation of an α-cyanocarbanion and subsequent highly enantioselective addition to aldimines.",

author = "Akira Saito and Naoya Kumagai and Masakatsu Shibasaki",

note = "Funding Information: This work was financially supported by KAKENHI (17H03025 and 18H04276 in Precisely Designed Catalysts with Customized Scaffolding) from JSPS and MEXT. We are grateful to Dr. Tomoyuki Kimura, Dr. Ryuichi Sawa, Ms. Yumiko Kubota, and Dr. Kiyoko Iijima at the Institute of Microbial Chemistry for technical support in NMR and X-ray crystallographic analysis. Publisher Copyright: Copyright {\textcopyright} 2019 American Chemical Society.",

year = "2019",

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doi = "10.1021/acs.orglett.9b02821",

language = "English",

volume = "21",

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journal = "Organic Letters",

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T1 - Direct Catalytic Asymmetric Addition of Acetonitrile to Aldimines

AU - Saito, Akira

AU - Kumagai, Naoya

AU - Shibasaki, Masakatsu

N1 - Funding Information: This work was financially supported by KAKENHI (17H03025 and 18H04276 in Precisely Designed Catalysts with Customized Scaffolding) from JSPS and MEXT. We are grateful to Dr. Tomoyuki Kimura, Dr. Ryuichi Sawa, Ms. Yumiko Kubota, and Dr. Kiyoko Iijima at the Institute of Microbial Chemistry for technical support in NMR and X-ray crystallographic analysis. Publisher Copyright: Copyright © 2019 American Chemical Society.

PY - 2019/10/18

Y1 - 2019/10/18

N2 - Despite significant advances in catalytic asymmetric reactions with decent stereocontrol, those using acetonitrile as a pronucleophile are often disregarded due to their low reactivity and insufficient enantioselectivity. Herein we report the resurgence of this reaction in the chemical toolbox with high enantioselectivity (avg. > 95% ee). The combined use of a Ni(II) complex ligated with a chiral biscarbene and tBuOK engages acetonitrile in the catalytic generation of an α-cyanocarbanion and subsequent highly enantioselective addition to aldimines.

AB - Despite significant advances in catalytic asymmetric reactions with decent stereocontrol, those using acetonitrile as a pronucleophile are often disregarded due to their low reactivity and insufficient enantioselectivity. Herein we report the resurgence of this reaction in the chemical toolbox with high enantioselectivity (avg. > 95% ee). The combined use of a Ni(II) complex ligated with a chiral biscarbene and tBuOK engages acetonitrile in the catalytic generation of an α-cyanocarbanion and subsequent highly enantioselective addition to aldimines.

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Direct Catalytic Asymmetric Addition of Acetonitrile to Aldimines

Abstract

ASJC Scopus subject areas

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