Direct Catalytic Asymmetric Addition of Alkylnitriles to Aldehydes with Designed Nickel–Carbene Complexes

Akira Saito; Shinya Adachi; Naoya Kumagai; Masakatsu Shibasaki

doi:10.1002/anie.202016690

Direct Catalytic Asymmetric Addition of Alkylnitriles to Aldehydes with Designed Nickel–Carbene Complexes

Akira Saito, Shinya Adachi, Naoya Kumagai, Masakatsu Shibasaki

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

Abstract

A direct catalytic asymmetric addition of acetonitrile to aldehydes that realizes over 90 % ee is the ultimate challenge in alkylnitrile addition chemistry. Herein, we report achieving high enantioselectivity by the strategic use of a sterically demanding Ni^II pincer carbene complex, which afforded highly enantioenriched β-hydroxynitriles. This highly atom-economical process paves the way for exploiting inexpensive acetonitrile as a promising C2 building block in a practical synthetic toolbox for asymmetric catalysis.

Original language	English
Pages (from-to)	8739-8743
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	60
Issue number	16
DOIs	https://doi.org/10.1002/anie.202016690
Publication status	Published - 2021 Apr 12
Externally published	Yes

Keywords

aldehydes
enantioselectivity
homogeneous catalysis
nickel
nitriles

ASJC Scopus subject areas

Catalysis
Chemistry(all)

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10.1002/anie.202016690

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title = "Direct Catalytic Asymmetric Addition of Alkylnitriles to Aldehydes with Designed Nickel–Carbene Complexes",

abstract = "A direct catalytic asymmetric addition of acetonitrile to aldehydes that realizes over 90 % ee is the ultimate challenge in alkylnitrile addition chemistry. Herein, we report achieving high enantioselectivity by the strategic use of a sterically demanding NiII pincer carbene complex, which afforded highly enantioenriched β-hydroxynitriles. This highly atom-economical process paves the way for exploiting inexpensive acetonitrile as a promising C2 building block in a practical synthetic toolbox for asymmetric catalysis.",

keywords = "aldehydes, enantioselectivity, homogeneous catalysis, nickel, nitriles",

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

note = "Funding Information: This work was financially supported by JSPS KAKENHI Grant Number JP20H03371 (Grant-in-Aid for Scientific Research (B)) to M.S., and JP19K22192 (Grant-in-Aid for Exploratory Research) and JP20H02746 (Grant-in-Aid for Scientific Research (B)) to N.K. We are grateful to Dr. Ryuichi Sawa, Ms. Yumiko Kubota, and Dr. Kiyoko Iijima at the Institute of Microbial Chemistry for technical support in NMR. Publisher Copyright: {\textcopyright} 2021 Wiley-VCH GmbH",

year = "2021",

month = apr,

day = "12",

doi = "10.1002/anie.202016690",

language = "English",

volume = "60",

pages = "8739--8743",

journal = "Angewandte Chemie - International Edition",

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T1 - Direct Catalytic Asymmetric Addition of Alkylnitriles to Aldehydes with Designed Nickel–Carbene Complexes

AU - Saito, Akira

AU - Adachi, Shinya

AU - Kumagai, Naoya

AU - Shibasaki, Masakatsu

N1 - Funding Information: This work was financially supported by JSPS KAKENHI Grant Number JP20H03371 (Grant-in-Aid for Scientific Research (B)) to M.S., and JP19K22192 (Grant-in-Aid for Exploratory Research) and JP20H02746 (Grant-in-Aid for Scientific Research (B)) to N.K. We are grateful to Dr. Ryuichi Sawa, Ms. Yumiko Kubota, and Dr. Kiyoko Iijima at the Institute of Microbial Chemistry for technical support in NMR. Publisher Copyright: © 2021 Wiley-VCH GmbH

PY - 2021/4/12

Y1 - 2021/4/12

N2 - A direct catalytic asymmetric addition of acetonitrile to aldehydes that realizes over 90 % ee is the ultimate challenge in alkylnitrile addition chemistry. Herein, we report achieving high enantioselectivity by the strategic use of a sterically demanding NiII pincer carbene complex, which afforded highly enantioenriched β-hydroxynitriles. This highly atom-economical process paves the way for exploiting inexpensive acetonitrile as a promising C2 building block in a practical synthetic toolbox for asymmetric catalysis.

AB - A direct catalytic asymmetric addition of acetonitrile to aldehydes that realizes over 90 % ee is the ultimate challenge in alkylnitrile addition chemistry. Herein, we report achieving high enantioselectivity by the strategic use of a sterically demanding NiII pincer carbene complex, which afforded highly enantioenriched β-hydroxynitriles. This highly atom-economical process paves the way for exploiting inexpensive acetonitrile as a promising C2 building block in a practical synthetic toolbox for asymmetric catalysis.

KW - aldehydes

KW - enantioselectivity

KW - homogeneous catalysis

KW - nickel

KW - nitriles

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JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

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ER -

Direct Catalytic Asymmetric Addition of Alkylnitriles to Aldehydes with Designed Nickel–Carbene Complexes

Abstract

Keywords

ASJC Scopus subject areas

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