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Cu‐Catalyzed Hydroxymethylation of Unactivated Alkyl Iodides with CO To Provide One‐Carbon‐Extended Alcohols
Author(s) -
Zhao Siling,
Mankad Neal P.
Publication year - 2018
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201801814
Subject(s) - carbonylation , alkyl , chemistry , catalysis , alcohol , iodide , reductive elimination , organic chemistry , primary (astronomy) , carbon monoxide , combinatorial chemistry , physics , astronomy
We have developed a reductive carbonylation method by which unactivated alkyl iodides can be hydroxymethylated to provide one‐carbon‐extended alcohol products under Cu‐catalyzed conditions. The method is tolerant of alkyl β‐hydrogen atoms, is robust towards a wide variety of functional groups, and was applied to primary, secondary, and tertiary alkyl iodide substrates. Mechanistic experiments indicate that the transformation proceeds by atom‐transfer carbonylation (ATC) of the alkyl iodide followed in tandem by two CuH‐mediated reductions in rapid succession. This radical mechanism renders the Cu‐catalyzed system complementary to precious‐metal‐catalyzed reductive carbonylation reactions.