2271-21-8Relevant academic research and scientific papers
Enantioselective Synthesis of α-Chiral Propargylic Silanes by Copper-Catalyzed 1,4-Selective Addition of Silicon Nucleophiles to Enyne-Type α,β,γ,δ-Unsaturated Acceptors
Mao, Wenbin,Oestreich, Martin
, p. 8096 - 8100 (2020)
A copper-catalyzed deconjugative addition of silicon nucleophiles to a broad range of enyne-type α,β,γ,δ-unsaturated acceptors with high enantiocontrol is reported. The method is 1,4-selective with hardly any formation of the 1,6-adduct. The double-bond geometry is shown to be critical for achieving this chemoselectivity: exclusive 1,4-addition for E and predominant 1,6-addition for Z. By this, E-configured enynoates, enynamides, and enynones have been converted to the corresponding α-chiral propargylic silanes with excellent enantiomeric excesses.
STEREOCONTROLLED SYNTHESIS OF NATURALLY-OCCURRING POLYACETYLENES CHARACTERIZED BY (E)-1-EN-3-YNE, (E)-1-EN-3,5-DIYNE, (1E,5E)-1,5-DIEN-3-YNE, AND (1E,7E)-1,7-DIEN-3,5-DIYNE MOIETIES
Carpita, Adriano,Neri, Dario,Rossi, Renzo
, p. 481 - 490 (2007/10/02)
A stereocontrolled synthesis of five naturally-occurring polyacetylenes, i.e. methyl (E)-5-(2-thienyl)-2-penten-4-ynoate, 9, (E)-N-methyl-N-(2-methylpropyl)-2-decen-4,6-diynamide, 10, (E)-1-(3-methyl-2-butenoyloxy)-2-decen-4,6-diyne, 11, (2E,6E)-1-acetoxy-2,6-decadien-4-yne, 12, and (2E,8E)-1-acetoxy-2,8-decadien-4,6-diyne, 13, is reported.The flexible strategy involves palladium(0)-copper(I) catalyzed coupling reactions to construct the carbon skeleton of the target molecules and to prepare an important C5 building block, i.e. (E)-2-penten-4-yn-1-ol, 21.This compound is also an useful intermediate to lipoxins A and B.A highly diastereoselective palladium-catalyzed carbon-carbon bond forming reaction, recently developed in our laboratory, has been used in a key synthetic step to compound 12.
