N-Silylation of amines mediated by Et3SiH/KOtBu

Fabrizio Palumbo; Simon Rohrbach; Tell Tuttle; John A. Murphy

doi:10.1002/hlca.201900235

N-Silylation of amines mediated by Et3SiH/KOtBu

Fabrizio Palumbo, Simon Rohrbach, Tell Tuttle, John A. Murphy

Pure And Applied Chemistry

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

13 Citations (Scopus)

43 Downloads (Pure)

Abstract

Silylation of primary and secondary amines is reported, using triethylsilane as the silylating reagent in the presence of potassium tert-butoxide (KOtBu). The reaction proceeds well in the presence of 0.2 equiv of KOtBu. In competition experiments, aniline is selectively silylated over aliphatic amines. Computational studies support a catalytic mechanism which is initiated by KOtBu interacting with the silane to form KH and silylated amine. The KH then takes over the role of base in the propagation of the cyclic mechanism, and deprotonates the amine. This reacts with R3SiH to afford the product R3SiNR’R” and regenerate KH.

Original language	English
Article number	e1900235
Pages (from-to)	1-8
Number of pages	8
Journal	Helvetica Chimica Acta
Volume	102
Issue number	12
Early online date	25 Oct 2019
DOIs	https://doi.org/10.1002/hlca.201900235
Publication status	Published - 1 Dec 2019

Keywords

KOtBu
N-silylation
dehydrogenation
transition metal-free
catalysis

Access to Document

10.1002/hlca.201900235

Palumbo-etal-HCA-2019-N-Silylation-of-amines-mediated-by-Et3SiH-KOtBuAccepted author manuscript, 757 KB

Cite this

@article{e3d502f09458434697b58914226323de,

title = "N-Silylation of amines mediated by Et3SiH/KOtBu",

abstract = "Silylation of primary and secondary amines is reported, using triethylsilane as the silylating reagent in the presence of potassium tert-butoxide (KOtBu). The reaction proceeds well in the presence of 0.2 equiv of KOtBu. In competition experiments, aniline is selectively silylated over aliphatic amines. Computational studies support a catalytic mechanism which is initiated by KOtBu interacting with the silane to form KH and silylated amine. The KH then takes over the role of base in the propagation of the cyclic mechanism, and deprotonates the amine. This reacts with R3SiH to afford the product R3SiNR{\textquoteright}R” and regenerate KH.",

keywords = "KOtBu, N-silylation, dehydrogenation, transition metal-free, catalysis",

author = "Fabrizio Palumbo and Simon Rohrbach and Tell Tuttle and Murphy, {John A.}",

note = "{\textcopyright} 2019 Wiley-VHCAAG,Zurich,Switzerland F. Palumbo, S. Rohrbach, T. Tuttle, J. A. Murphy, HCA 2019, 102, e1900235.",

year = "2019",

month = dec,

day = "1",

doi = "10.1002/hlca.201900235",

language = "English",

volume = "102",

pages = "1--8",

journal = "Helvetica Chimica Acta",

issn = "0018-019X",

number = "12",

}

TY - JOUR

T1 - N-Silylation of amines mediated by Et3SiH/KOtBu

AU - Palumbo, Fabrizio

AU - Rohrbach, Simon

AU - Tuttle, Tell

AU - Murphy, John A.

PY - 2019/12/1

Y1 - 2019/12/1

N2 - Silylation of primary and secondary amines is reported, using triethylsilane as the silylating reagent in the presence of potassium tert-butoxide (KOtBu). The reaction proceeds well in the presence of 0.2 equiv of KOtBu. In competition experiments, aniline is selectively silylated over aliphatic amines. Computational studies support a catalytic mechanism which is initiated by KOtBu interacting with the silane to form KH and silylated amine. The KH then takes over the role of base in the propagation of the cyclic mechanism, and deprotonates the amine. This reacts with R3SiH to afford the product R3SiNR’R” and regenerate KH.

AB - Silylation of primary and secondary amines is reported, using triethylsilane as the silylating reagent in the presence of potassium tert-butoxide (KOtBu). The reaction proceeds well in the presence of 0.2 equiv of KOtBu. In competition experiments, aniline is selectively silylated over aliphatic amines. Computational studies support a catalytic mechanism which is initiated by KOtBu interacting with the silane to form KH and silylated amine. The KH then takes over the role of base in the propagation of the cyclic mechanism, and deprotonates the amine. This reacts with R3SiH to afford the product R3SiNR’R” and regenerate KH.

KW - KOtBu

KW - N-silylation

KW - dehydrogenation

KW - transition metal-free

KW - catalysis

UR - https://onlinelibrary.wiley.com/journal/15222675

U2 - 10.1002/hlca.201900235

DO - 10.1002/hlca.201900235

M3 - Article

SN - 0018-019X

VL - 102

SP - 1

EP - 8

JO - Helvetica Chimica Acta

JF - Helvetica Chimica Acta

IS - 12

M1 - e1900235

ER -

N-Silylation of amines mediated by Et3SiH/KOtBu

Abstract

Keywords

Access to Document

Other files and links

Fingerprint

Data for: "N-Silylation of Amines Mediated by the Et3SiH/KOtBu System"

Cite this

N-Silylation of amines mediated by Et3SiH/KOtBu

Abstract

Keywords

Access to Document

Other files and links

Fingerprint

Datasets

Data for: "N-Silylation of Amines Mediated by the Et3SiH/KOtBu System"

Cite this