Zirconium/Nickel-Mediated One-Pot Ketone Synthesis

Yanran Ai; Ning Ye; Qiaoyi Wang; Kenzo Yahata; Yoshito Kishi

doi:10.1002/anie.201705520

Zirconium/Nickel-Mediated One-Pot Ketone Synthesis

Angew Chem Int Ed Engl. 2017 Aug 28;56(36):10791-10795. doi: 10.1002/anie.201705520. Epub 2017 Jul 28.

Authors

Yanran Ai¹, Ning Ye¹, Qiaoyi Wang¹, Kenzo Yahata¹, Yoshito Kishi¹

Affiliation

¹ Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA, 02138, USA.

PMID: 28683181
DOI: 10.1002/anie.201705520

Abstract

A zirconium/nickel-mediated one-pot synthesis of ketones is reported. In the presence of Zn or Mn, Cp₂ ZrCl₂ was found to dramatically accelerate the coupling and suppress side product formation via an I→SPy displacement at the same time. Unlike Zn/Pd- and Fe/Cu-mediated one-pot ketone syntheses, the new method is effective for nucleophiles bearing OR or equivalent functional groups at the α-position. A mechanism comprising a nickel catalytic cycle, a zirconium catalytic cycle, and Zr→Ni transmetalation is proposed, and Cp₂ ZrCl₂ and/or low-valent Zr species are suggested to play crucial dual roles.

Keywords: ketones; nickel; radical reactions; transition-metal catalysis; zirconium.

Publication types

Research Support, Non-U.S. Gov't