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. 2013 Jan 9;135(1):66-9.
doi: 10.1021/ja3104389. Epub 2012 Dec 18.

Rh(III)-catalyzed regioselective synthesis of pyridines from alkenes and α,β-unsaturated oxime esters

Jamie M Neely  1 , Tomislav Rovis
Affiliations

Rh(III)-catalyzed regioselective synthesis of pyridines from alkenes and α,β-unsaturated oxime esters

Jamie M Neely et al. J Am Chem Soc. .

Abstract

α,β-Unsaturated O-pivaloyl oximes are coupled to alkenes by Rh(III) catalysis to afford substituted pyridines. The reaction with activated alkenes is exceptionally regioselective and high-yielding. Mechanistic studies suggest that heterocycle formation proceeds via reversible C-H activation, alkene insertion, and a C-N bond formation/N-O bond cleavage process.

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Conflict of interest statement

Funding Sources

No competing financial interests have been declared.

Figures

Figure 1
Figure 1
Two possible pathways for C-N bond formation.
Scheme 1
Scheme 1
Proposed Reaction Mechanism
Chart 1
Chart 1. Oxime Ester Scopea
aConditions: 1 (0.21 mmol), 2a (0.25 mmol), [RhCp*Cl2]2 (0.005 mmol) and AgOAc (0.44 mmol) in 0.7 mL DCE/AcOH (2:1) for 14h. b0.12 mmol scale.
Chart 2
Chart 2. Activated Alkene Scopea
aConditions: see Chart 1. For 1g: 1.05 equiv 2. b1.2 equiv 1c. c75 °C.
See this image and copyright information in PMC

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