z-logo
Premium
Facile Synthesis of Cyanide and Isocyanides from CO
Author(s) -
Xu Maotong,
Kooij Bastiaan,
Wang Tongtong,
Lin Jack H.,
Qu ZhengWang,
Grimme Stefan,
Stephan Douglas W.
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202105909
Subject(s) - isocyanide , chemistry , steric effects , substituent , cyanide , aryl , silylation , alkyl , salt (chemistry) , medicinal chemistry , alkali metal , stereochemistry , organic chemistry , catalysis
The reaction of K[N(SiMe 3 ) 2 ] with 13 CO proceeds in C 6 D 6 or THF affording K 13 CN and O(SiMe 3 ) 2 under mild conditions as confirmed by crystallographic characterization of K(18‐crown‐6)CN. Similarly reaction of the alkali metal amides, M[N(SiR 3 )R′] (M=Li, K; R=Ph, Me; R′=alkyl, aryl) provides the corresponding 13 C labeled isocyanide RN 13 C and MOSiR 3 , generally in high yields. In some instances, the use of the sterically bulky Ph 3 Si‐substituent is required to preclude 1,2‐silyl migration affording the silylcarbamoyl salt M[Me 3 SiC(O)NR′]. These reactions have been used to obtain 19 examples of 13 C labelled isocyanides, and several examples of gram scale reactions are reported. The mechanism of the reactions is probed via reliable DFT calculations.

This content is not available in your region!

Continue researching here.

Having issues? You can contact us here