Premium
Practical Reagents and Methods for Nucleophilic and Electrophilic Phosphorothiolations
Author(s) -
Kovács Szabolcs,
Bayarmagnai Bilguun,
Aillerie Alexandre,
Gooßen Lukas J.
Publication year - 2018
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201701549
Subject(s) - chemistry , umpolung , reagent , electrophile , nucleophile , combinatorial chemistry , yield (engineering) , alkyl , tetramethylammonium , halide , organic chemistry , medicinal chemistry , catalysis , ion , materials science , metallurgy
New late‐stage phosphorothiolation methods are disclosed that allow the efficient transfer of SP(O)(OR) 2 groups to diversely functionalized substrates using nucleophilic and electrophilic reagents. The nucleophilic reagent, tetramethylammonium O,O ‐dimethyl phosphorothioate, was synthesized in near‐quantitative yield from Me 3 SiP(O)(OMe) 2 , elemental sulfur and Me 4 NF. Its umpolung with N ‐bromophthalimide provided the electrophilic reagent, O,O ‐dimethyl‐ S ‐( N ‐phthalimido)phosphorothioate. Complementary methods based on these reagents enable the phosphorothiolation of diversely functionalized alkyl halides, arenediazonium salts, arylboronic acids and electron‐rich arenes in good yields under mild conditions.