Facile Synthesis of Cyanide and Isocyanides from CO

The reaction of K[N(SiMe3)2] with 13CO proceeds in C6D6 or THF affording K13CN and O(SiMe3)2 under mild conditions as confirmed by crystallographic characterization of K(18‐crown‐6)CN. Similarly reaction of the alkali metal amides, M[N(SiR3)R′] (M=Li, K; R=Ph, Me; R′=alkyl, aryl) provides the corres...

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Published in:Angewandte Chemie International Edition 2021-07, Vol.60 (31), p.16965-16969
Main Authors: Xu, Maotong, Kooij, Bastiaan, Wang, Tongtong, Lin, Jack H., Qu, Zheng‐Wang, Grimme, Stefan, Stephan, Douglas W.
Format: Article
Language:English
Subjects:
13C labelled iso cyanides
Alkali metals
Amides
carbon monoxide
Crystallography
cyanide
Cyanides
isotopic labeling
small molecule activation
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Summary:The reaction of K[N(SiMe3)2] with 13CO proceeds in C6D6 or THF affording K13CN and O(SiMe3)2 under mild conditions as confirmed by crystallographic characterization of K(18‐crown‐6)CN. Similarly reaction of the alkali metal amides, M[N(SiR3)R′] (M=Li, K; R=Ph, Me; R′=alkyl, aryl) provides the corresponding 13C labeled isocyanide RN13C and MOSiR3, generally in high yields. In some instances, the use of the sterically bulky Ph3Si‐substituent is required to preclude 1,2‐silyl migration affording the silylcarbamoyl salt M[Me3SiC(O)NR′]. These reactions have been used to obtain 19 examples of 13C labelled isocyanides, and several examples of gram scale reactions are reported. The mechanism of the reactions is probed via reliable DFT calculations. The reactions of K[N(SiMe3)2] with 13CO affords K13CN and O(SiMe3)2 under mild conditions. DFT calculations affirmed this reaction proceeds via an isocyanide intermediate. This was confirmed experimentally as the alkali metal amides, M[N(SiR3)R′] (M=Li, K; R=Ph, Me; R′=alkyl, aryl) are shown to provide a facile route to the 19 13C labeled isocyanide RN13C and MOSiR3 generally in high yields.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202105909