Palladium-catalyzed γ-selective and stereospecific allyl-aryl coupling between acyclic allylic esters and arylboronic acids

Hirohisa Ohmiya, Yusuke Makida, Dong Li, Masahito Tanabe, Masaya Sawamura

Research output: Contribution to journalArticle

105 Citations (Scopus)

Abstract

Reactions between acyclic (E)-allylic acetates and arylboronic acids in the presence of a palladium catalyst prepared from Pd(OAc)2, phenanthroline (or bipyridine), and AgSbF6 (1:1.2:1) proceeded with excellent γ-selectivity to afford allyl-aryl coupling products with E-configuration. The reactions of α-chiral allylic acetates took place with excellent α-to-γ chirality transfer with syn stereochemistry to give allylated arenes with a stereogenic center at the benzylic position. The reaction tolerated a broad range of functional groups in both the allylic acetates and the arylboronic acids. Furthermore, γ-arylation of cinnamyl alcohol derivatives afforded gem-diarylalkane derivatives containing an unconjugated alkenic substituent. The synthetic utility of this method was demonstrated by its utilization in an efficient synthesis of (+)-sertraline, an antidepressant agent. The observed γ-regioselectivity and E-1,3-syn stereochemistry were rationalized based on a Pd(II) mechanism involving transmetalation between a cationic mono(acyloxo)palladium(II) complex and arylboronic acid, and directed carbopalladation followed by syn-β-acyloxy elimination. The results of stoichiometric reactions of palladium complexes related to possible intermediates were fully consistent with the proposed mechanism.

Original languageEnglish
Pages (from-to)879-889
Number of pages11
JournalJournal of the American Chemical Society
Volume132
Issue number2
DOIs
Publication statusPublished - Jan 20 2010

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Palladium
Esters
Stereochemistry
Acetates
Acids
Gems
Derivatives
Sertraline
Regioselectivity
Phenanthrolines
Chirality
Functional groups
Antidepressive Agents
Alcohols
Catalysts

All Science Journal Classification (ASJC) codes

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

Cite this

Palladium-catalyzed γ-selective and stereospecific allyl-aryl coupling between acyclic allylic esters and arylboronic acids. / Ohmiya, Hirohisa; Makida, Yusuke; Li, Dong; Tanabe, Masahito; Sawamura, Masaya.

In: Journal of the American Chemical Society, Vol. 132, No. 2, 20.01.2010, p. 879-889.

Research output: Contribution to journalArticle

Ohmiya, Hirohisa ; Makida, Yusuke ; Li, Dong ; Tanabe, Masahito ; Sawamura, Masaya. / Palladium-catalyzed γ-selective and stereospecific allyl-aryl coupling between acyclic allylic esters and arylboronic acids. In: Journal of the American Chemical Society. 2010 ; Vol. 132, No. 2. pp. 879-889.
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