Premium
Asymmetric Synthesis of Primary Amines by Nucleophilic Addition of Alkyllithium Compounds to Aldehyde SAMP/RAMP Hydrazones
Author(s) -
Enders Dieter,
Nübling Christoph,
Schubert Heinrich
Publication year - 1997
Publication title -
liebigs annalen
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 0947-3440
DOI - 10.1002/jlac.199719970608
Subject(s) - chemistry , aldehyde , alkylation , yield (engineering) , primary (astronomy) , medicinal chemistry , nucleophilic addition , nucleophile , hydrazone , derivative (finance) , bond cleavage , organic chemistry , stereochemistry , catalysis , materials science , physics , astronomy , economics , financial economics , metallurgy
The aldehydes 1 or 5 are converted to the SAMP hydrazones 2 or the α‐alkylated SAMP hydrazones 7 and treated with organolithium compounds at low temperature. Cleavage of the NN bond of the resulting hydrazines 3 and 8 with Raney‐Ni/H 2 , or of the N ‐methoxycarbonylhydrazines 9 with Li/NH 3 , yield the amines 4 with 61–90% ee, the amines 11 with 45–96% de and 93 → 99% ee. The absolute configuration of the amines 11 was established by X‐ray analysis of an appropriate MTPA derivative.