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Batch and Continuous‐Flow One‐Pot Processes using Amine Diazotization to Produce Silylated Diazo Reagents
Author(s) -
Audubert Clément,
Gamboa Marin Oscar Javier,
Lebel Hélène
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201612235
Subject(s) - methylamines , diazomethane , diazo , chemistry , reagent , continuous flow , amine gas treating , flow chemistry , organic chemistry , cycloaddition , catalysis , rhodium , combinatorial chemistry , cyclopropene , silanol , physics , mechanics
A novel synthesis of trimethylsilyldiazomethane (TMSCHN 2 ) by diazotization of trimethylsilylmethylamine (TMSCH 2 NH 2 ) is reported using batch and continuous flow synthesis. The latter affords a daily production of 275 g (2.4 mol) of TMSCHN 2 . Other silylated methylamines were also successfully reacted under the developed reaction conditions to furnish various silicon‐bearing diazomethane reagents. The applicability of the process is highlighted by disclosure of batch and continuous flow one‐pot esterification and 1,3‐dipolar cycloaddition processes. Furthermore, the high‐yielding esterification of carboxylic acids with silylated and substituted methylamines in continuous flow is disclosed. Finally, work‐up and purification procedures are reported for the preparation of a 2‐MeTHF solution of TMSCHN 2 , which can be used in rhodium‐catalyzed methylenation and homologation reactions.