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Nitroprolinates as Nucleophiles in Michael‐type Additions and Acylations. Synthesis of Enantiomerically Enriched Fused Amino‐pyrrolidino‐[1,2‐ a ]pyrazinones and ‐diketopiperazines
Author(s) -
GarcíaMingüens Eduardo,
Selva Verónica,
Larrañaga Olatz,
Nájera Carmen,
Sansano José M.,
Cózar Abel
Publication year - 2020
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201902382
Subject(s) - diketopiperazines , enantioselective synthesis , chemistry , michael reaction , nucleophile , phosphoramidite , acylation , organic chemistry , benzoic acid , amination , alkene , combinatorial chemistry , medicinal chemistry , catalysis , dna , biochemistry , oligonucleotide
The enantioselective formation of nitroprolinates followed by diastereoselective Michael‐type addition onto a second unit of the nitro alkene is studied. The reaction occurred in a one pot‐sequential process controlled by the chiral phosphoramidite⋅silver benzoate complex. The origin of the high diastereoselectivity is studied by DFT computational analysis where the crucial effect of the benzoic acid is justified. The employment of this strategy to the preparation of pyrazine‐2‐ones is also surveyed, as well as the preparation of diketopiperazines from enantiomerically enriched exo‐ prolinates using conventional N ‐acylation‐amination‐cyclization steps.