Chemoselective silylative reduction of conjugated nitriles under metal-free catalytic conditions: β-silyl amines and enamines

Narasimhulu Gandhamsetty; Juhyeon Park; Jinseong Jeong; Sung Woo Park; Sehoon Park; Sukbok Chang

doi:10.1002/anie.201502366

Chemoselective silylative reduction of conjugated nitriles under metal-free catalytic conditions: β-silyl amines and enamines

Narasimhulu Gandhamsetty, Juhyeon Park, Jinseong Jeong, Sung Woo Park, Sehoon Park, Sukbok Chang^*

^*Corresponding author for this work

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

67 Scopus citations

Abstract

Abstract The B(C₆F₅)₃-catalyzed silylative reduction of conjugated nitriles has been developed to afford synthetically valuable β-silyl amines. The reaction is chemoselective and proceeds under mild conditions. Mechanistic elucidation indicates that it proceeds by rapid double hydrosilylation of the conjugated nitrile to an enamine intermediate which is subsequently reduced to the β-silyl amine, thus forming a new C(sp³)-Si bond. Based on this mechanistic understanding, a preparative route to enamines was also established using bulky silanes. Triple whammy: The B(C₆F₅)₃-catalyzed silylative reduction of conjugated nitriles has been developed to afford synthetically valuable β-silyl amines. Based on the mechanistic understanding, a preparative route to enamines was also established using bulky silanes. The reaction is chemoselective, has a broad scope, and proceeds under mild reaction conditions. The mechanism of the triple hydrosilylation is discussed.

Original language	English
Pages (from-to)	6832-6836
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	54
Issue number	23
DOIs	https://doi.org/10.1002/anie.201502366
State	Published - 1 Jun 2015
Externally published	Yes

Keywords

boron
conjugation
hydrosilylation
reduction
synthetic methods

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title = "Chemoselective silylative reduction of conjugated nitriles under metal-free catalytic conditions: β-silyl amines and enamines",

abstract = "Abstract The B(C6F5)3-catalyzed silylative reduction of conjugated nitriles has been developed to afford synthetically valuable β-silyl amines. The reaction is chemoselective and proceeds under mild conditions. Mechanistic elucidation indicates that it proceeds by rapid double hydrosilylation of the conjugated nitrile to an enamine intermediate which is subsequently reduced to the β-silyl amine, thus forming a new C(sp3)-Si bond. Based on this mechanistic understanding, a preparative route to enamines was also established using bulky silanes. Triple whammy: The B(C6F5)3-catalyzed silylative reduction of conjugated nitriles has been developed to afford synthetically valuable β-silyl amines. Based on the mechanistic understanding, a preparative route to enamines was also established using bulky silanes. The reaction is chemoselective, has a broad scope, and proceeds under mild reaction conditions. The mechanism of the triple hydrosilylation is discussed.",

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author = "Narasimhulu Gandhamsetty and Juhyeon Park and Jinseong Jeong and Park, {Sung Woo} and Sehoon Park and Sukbok Chang",

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doi = "10.1002/anie.201502366",

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T1 - Chemoselective silylative reduction of conjugated nitriles under metal-free catalytic conditions

T2 - β-silyl amines and enamines

AU - Gandhamsetty, Narasimhulu

AU - Park, Juhyeon

AU - Jeong, Jinseong

AU - Park, Sung Woo

AU - Park, Sehoon

AU - Chang, Sukbok

PY - 2015/6/1

Y1 - 2015/6/1

N2 - Abstract The B(C6F5)3-catalyzed silylative reduction of conjugated nitriles has been developed to afford synthetically valuable β-silyl amines. The reaction is chemoselective and proceeds under mild conditions. Mechanistic elucidation indicates that it proceeds by rapid double hydrosilylation of the conjugated nitrile to an enamine intermediate which is subsequently reduced to the β-silyl amine, thus forming a new C(sp3)-Si bond. Based on this mechanistic understanding, a preparative route to enamines was also established using bulky silanes. Triple whammy: The B(C6F5)3-catalyzed silylative reduction of conjugated nitriles has been developed to afford synthetically valuable β-silyl amines. Based on the mechanistic understanding, a preparative route to enamines was also established using bulky silanes. The reaction is chemoselective, has a broad scope, and proceeds under mild reaction conditions. The mechanism of the triple hydrosilylation is discussed.

AB - Abstract The B(C6F5)3-catalyzed silylative reduction of conjugated nitriles has been developed to afford synthetically valuable β-silyl amines. The reaction is chemoselective and proceeds under mild conditions. Mechanistic elucidation indicates that it proceeds by rapid double hydrosilylation of the conjugated nitrile to an enamine intermediate which is subsequently reduced to the β-silyl amine, thus forming a new C(sp3)-Si bond. Based on this mechanistic understanding, a preparative route to enamines was also established using bulky silanes. Triple whammy: The B(C6F5)3-catalyzed silylative reduction of conjugated nitriles has been developed to afford synthetically valuable β-silyl amines. Based on the mechanistic understanding, a preparative route to enamines was also established using bulky silanes. The reaction is chemoselective, has a broad scope, and proceeds under mild reaction conditions. The mechanism of the triple hydrosilylation is discussed.

KW - boron

KW - conjugation

KW - hydrosilylation

KW - reduction

KW - synthetic methods

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M3 - 文章

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ER -

Chemoselective silylative reduction of conjugated nitriles under metal-free catalytic conditions: β-silyl amines and enamines

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Keywords

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