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Ruthenium–Porphyrin‐Catalyzed Diastereoselective Intramolecular Alkyl Carbene Insertion into CH Bonds of Alkyl Diazomethanes Generated In Situ from N ‐Tosylhydrazones
Author(s) -
Reddy Annapureddy Rajasekar,
Zhou CongYing,
Guo Zhen,
Wei Jinhu,
Che ChiMing
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201408102
Subject(s) - chemistry , intramolecular force , ruthenium , carbene , porphyrin , alkyl , catalysis , yield (engineering) , photochemistry , medicinal chemistry , combinatorial chemistry , stereochemistry , organic chemistry , materials science , metallurgy
With a ruthenium–porphyrin catalyst, alkyl diazomethanes generated in situ from N ‐tosylhydrazones efficiently underwent intramolecular C(sp 3 )H insertion of an alkyl carbene to give substituted tetrahydrofurans and pyrrolidines in up to 99 % yield and with up to 99:1 cis selectivity. The reaction displays good tolerance of many functionalities, and the procedure is simple without the need for slow addition with a syringe pump. From a synthetic point of view, the CH insertion of N ‐tosylhydrazones can be viewed as reductive coupling between a CO bond and a CH bond to form a new CC bond, since N ‐tosylhydrazones can be readily prepared from carbonyl compounds. This reaction was successfully applied in a concise synthesis of (±)‐pseudoheliotridane.