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Inside Back Cover: Thioaldehydes from Aldehyde–Hydrogen Sulfide Interaction Under Organocatalysis (Chem. Eur. J. 11/2017)
Author(s) -
Kumar Manoj,
Francisco Joseph S.
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Reports
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201605714
Subject(s) - chemistry , aldehyde , nucleophile , organocatalysis , hydrogen sulfide , methanogen , catalysis , sulfide , mechanism (biology) , organic chemistry , combinatorial chemistry , enantioselective synthesis , sulfur , philosophy , epistemology , methane
Traditionally, thioaldehydes are believed to be formed by the nucleophilic attack of bisulfide anion on carbonyl compounds. In the theoretical calculations reported herein, we suggest a new mechanism for their formation that involves an interaction between hydrogen sulfide and an aldehyde. Under acid catalysis, the reaction not only involves moderate barriers, but thioaldehyde is also formed in a hydrogen‐bonded state, which is more stable than separated product and acid catalyst. This may have implications for the solution‐phase synthesis of simpler thioaldehydes, which has been a significant challenge. These results may also explain the enzyme mechanism of the aspartate semialdehyde→aspartate semithioaldehyde conversion, which is a key biosynthetic reaction in methanogen archaea. More information can be found in the Communication by J. S. Francisco and M. Kumar on page 2522 ff.