Copper-Catalyzed γ-Selective and Stereospecific Allylic Cross-Coupling with Secondary Alkylboranes

Yuto Yasuda; Kazunori Nagao; Yoshinori Shido; Seiji Mori; Hirohisa Ohmiya; Masaya Sawamura

doi:10.1002/chem.201501055

Copper-Catalyzed γ-Selective and Stereospecific Allylic Cross-Coupling with Secondary Alkylboranes

Chemistry. 2015 Jun 26;21(27):9666-70. doi: 10.1002/chem.201501055. Epub 2015 May 26.

Authors

Yuto Yasuda¹, Kazunori Nagao¹, Yoshinori Shido¹, Seiji Mori², Hirohisa Ohmiya³, Masaya Sawamura⁴

Affiliations

¹ Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810 (Japan), ;http://wwwchem.sci.hokudai.ac.jp/∼orgmet/index.php.
² Faculty of Science, Ibaraki University, Mito 310-8512 (Japan).
³ Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810 (Japan), ;http://wwwchem.sci.hokudai.ac.jp/∼orgmet/index.php. ohmiya@sci.hokudai.ac.jp.
⁴ Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810 (Japan), ;http://wwwchem.sci.hokudai.ac.jp/∼orgmet/index.php. sawamura@sci.hokudai.ac.jp.

PMID: 26013036
DOI: 10.1002/chem.201501055

Abstract

The scope of the copper-catalyzed coupling reactions between organoboron compounds and allylic phosphates is expanded significantly by employing triphenylphosphine as a ligand for copper, allowing the use of secondary alkylboron compounds. The reaction proceeds with complete γ-E-selectivity and preferential 1,3-syn stereoselectivity. The reaction of γ-silicon-substituted allylic phosphates affords enantioenriched α-stereogenic allylsilanes.

Keywords: allylic substitution; copper catalysis; coupling; secondary alkylborane; stereoselectivity.