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A General Synthesis of Sphinganines through Multicomponent Catalytic Asymmetric Aziridination
Author(s) -
Mukherjee Munmun,
Zhou Yubai,
Gupta Anil K.,
Guan Yong,
Wulff William D.
Publication year - 2014
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201301766
Subject(s) - aziridine , chemistry , enantiopure drug , nucleophile , ethyl diazoacetate , enantiomeric excess , diastereomer , enantiomer , aldehyde , amine gas treating , walden inversion , enantioselective synthesis , ring (chemistry) , catalysis , stereochemistry , organic chemistry , cyclopropanation
A catalytic asymmetric synthesis of all four stereoisomers of sphinganine is described starting from hexadecanal. Utilizing either the ( R ) or ( S ) enantiomer of a BOROX catalyst, a multicomponent reaction of this aldehyde with an amine and ethyl diazoacetate gives rise to enantiomeric aziridine‐2‐carboxylates. Access to all diastereomers of sphinganine is realized upon ring opening of the enantiopure aziridine‐2‐carboxylate at the C‐3 position by direct S N 2 attack of an oxygen nucleophile, which occurs with inversion of configuration and by ring expansion of an N ‐acyl aziridine to an oxazolidinone and then hydrolysis. Overall, this process results in the formal ring opening of the aziridine with an oxygen nucleophile with retention of configuration.