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Investigation of (Me 4 N)SCF 3 as a Stable, Solid and Safe Reservoir for S=CF 2 as a Surrogate for Thiophosgene
Author(s) -
Scattolin Thomas,
Pu Maoping,
Schoenebeck Franziska
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201705240
Subject(s) - electrophile , reactivity (psychology) , nucleophile , chemistry , rationalization (economics) , combinatorial chemistry , computational chemistry , selectivity , scale (ratio) , organic chemistry , catalysis , physics , medicine , philosophy , alternative medicine , epistemology , pathology , quantum mechanics
While thiophosgene finds widespread usage on a multi‐ton scale, its fluorinated counterpart S=CF 2 is essentially unexplored in synthesis. Using experimental reactivity tests, ReactIR and computational techniques, we herein showcase that the solid (Me 4 N)SCF 3 functions as a safe reservoir for S=CF 2 . A key feature is that the reactive electrophile is not simply released over time, but instead is liberated under activation with a protic nucleophile. The reactivity of S=CF 2 is mild, allowing large‐scale and late‐stage synthetic applications without special reaction control. The mechanism was fully elucidated, including a rationalization of the role of the Me 4 N cation and the origins of selectivity.