Copper-catalyzed enantioselective allylic alkylation of terminal alkyne pronucleophiles

Ayumi Harada, Yusuke Makida, Tatsunori Sato, Hirohisa Ohmiya, Masaya Sawamura

Research output: Contribution to journalArticle

40 Citations (Scopus)

Abstract

The copper-catalyzed enantioselective allylic alkylation of terminal alkynes with primary allylic phosphates was developed by the use of a new chiral N-heterocyclic carbene ligand bearing a phenolic hydroxy group at the ortho position of one of the two N-aryl groups. This reaction occurred with excellent γ-branch regioselectivity and high enantioselectivity, forming a controlled stereogenic center at the allylic/propargylic position. Various terminal alkynes, including silyl, aliphatic, and aromatic alkynes, could be used directly without premetalation of the C(sp)-H bond. On the basis of the results of experiments using an isomeric secondary allylic phosphate, which gave a branched product through an α-selective substitution reaction with retention of configuration, a reaction pathway involving 1,3-allylic migration of Cu in a ([σ + π]-allyl)copper(III) species is proposed.

Original languageEnglish
Pages (from-to)13932-13939
Number of pages8
JournalJournal of the American Chemical Society
Volume136
Issue number39
DOIs
Publication statusPublished - Sep 12 2014
Externally publishedYes

Fingerprint

Alkynes
Alkylation
Copper
Phosphates
Bearings (structural)
Regioselectivity
Enantioselectivity
Substitution reactions
Ligands
Experiments

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Copper-catalyzed enantioselective allylic alkylation of terminal alkyne pronucleophiles. / Harada, Ayumi; Makida, Yusuke; Sato, Tatsunori; Ohmiya, Hirohisa; Sawamura, Masaya.

In: Journal of the American Chemical Society, Vol. 136, No. 39, 12.09.2014, p. 13932-13939.

Research output: Contribution to journalArticle

Harada, Ayumi ; Makida, Yusuke ; Sato, Tatsunori ; Ohmiya, Hirohisa ; Sawamura, Masaya. / Copper-catalyzed enantioselective allylic alkylation of terminal alkyne pronucleophiles. In: Journal of the American Chemical Society. 2014 ; Vol. 136, No. 39. pp. 13932-13939.
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