Rhodium(III)-Catalyzed Synthesis
of Pyridines from α,β-Unsaturated Ketoximes
and Internal Alkynes

Pei Chui Too; Toshiharu Noji; Ying Jie Lim; Xingwei Li; Shunsuke Chiba

doi:10.1055/s-0031-1289556

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Synlett 2011(19): 2789-2794
DOI: 10.1055/s-0031-1289556

LETTER

Rhodium(III)-Catalyzed Synthesis of Pyridines from α,β-Unsaturated Ketoximes and Internal Alkynes

Pei Chui Too^a, Toshiharu Noji^b, Ying Jie Lim^a, Xingwei Li*^c, Shunsuke Chiba*^a
^a Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, 637371 Singapore, Singapore
Fax: +6567911961; e-Mail: shunsuke@ntu.edu.sg;
^b Graduate School of Pharmaceutical Sciences, Tohoku University, Aramaki, Aoba-ku, Sendai 980-8578, Japan
^c Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, P. R. of China
e-Mail: xwli@dicp.ac.cn;

Further Information

Publication History

Received 1 September 2011
Publication Date:
25 October 2011 (online)

Abstract
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Supplementary Material

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Abstract

A method for the synthesis of highly substituted pyridines from α,β-unsaturated oximes and internal alkynes has been developed using [Cp*RhCl₂]₂-CsOPiv as the catalyst system. The present transformation is carried out by a redox-neutral sequence of vinylic C-H rhodation, alkyne insertion, and C-N bond formation of the putative vinyl rhodium intermediate with the oxime nitrogen, where the N-O bond of oxime derivatives could work as an internal oxidant to maintain the catalytic cycle.

Key words

pyridines - oximes - alkynes - rhodium - C-H activation

Supporting Information

References and Notes

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12

The formation of 4aa could result in generation of rhodium(I) species, which should be re-oxidized to rhodium(III) by air (O₂) to maintain the catalytic turnover.

14

General Procedure (Table 1, Entry 6)
To a MeOH solution (2.5 mL) of (2E,3E)-4-phenylbut-3-
en-2-one oxime (1a, 80.5 mg, 0.50 mmol) and diphenyl-acetylene (2a, 106.9 mg, 0.60 mmol) were added [Cp*RhCl₂]₂ (7.7 mg, 0.0125 mmol) and CsOPiv (35.1 mg, 0.15 mmol), and the reaction mixture was stirred at 60 ˚C under air for 7 h. After cooled to r.t., the solvent was removed in vacuo, and the resulting crude material was subjected to flash column chromatography (hexane-EtOAc = 90:10) to afford 6-methyl-2,3,4-triphenylpyridine (3aa, 126.4 mg, 0.393 mmol) in 79% yield.

Supplementary Material

Supporting Information