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Sequential Copper‐Catalyzed Rearrangement–Allylic Substitution of Bicyclic Hydrazines with Grignard Reagents
Author(s) -
Crotti Stefano,
Bertolini Ferruccio,
Macchia Franco,
Pineschi Mauro
Publication year - 2009
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.200900037
Subject(s) - chemistry , allylic rearrangement , regioselectivity , reagent , trifluoromethanesulfonate , tsuji–trost reaction , medicinal chemistry , bicyclic molecule , alkylation , catalysis , copper , stereochemistry , organic chemistry
The problem of the synthesis of trans‐ 1,4‐disubstituted hydrazino‐ and aminocyclopentenes has been resolved by a sequential copper‐catalyzed rearrangement–allylic alkylation of 2,3‐diazabicyclo[2.2.1]heptenes. The cis ‐fused 5,5‐membered allylic carbazate which is formed in situ by a novel copper(II) triflate [Cu(OTf) 2 ]/(±)‐BINAP‐catalyzed rearrangement, can be alkylated with a broad spectrum of Grignard reagents with a predominant S N 2′‐regioselectivity. The N‐Boc protecting group proved to be optimal as regards yields, reaction times and regioselectivities.