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. 2012 Aug 3;77(15):6463-72.
doi: 10.1021/jo300973r. Epub 2012 Jul 25.

Rhodium-catalyzed carbonylation of cyclopropyl substituted propargyl esters: a tandem 1,3-acyloxy migration [5 + 1] cycloaddition

Dongxu Shu  1 , Xiaoxun Li, Min Zhang, Patrick J Robichaux, Ilia A Guzei, Weiping Tang
Affiliations

Rhodium-catalyzed carbonylation of cyclopropyl substituted propargyl esters: a tandem 1,3-acyloxy migration [5 + 1] cycloaddition

Dongxu Shu et al. J Org Chem. .

Abstract

We have developed two different types of tandem reactions for the synthesis of highly functionalized cyclohexenones from cyclopropyl substituted propargyl esters. Both reactions were initiated by rhodium-catalyzed Saucy-Marbet 1,3-acyloxy migration. The resulting cyclopropyl substituted allenes derived from acyloxy migration then underwent [5 + 1] cycloaddition with CO. The acyloxy group not only eased the access to allene intermediates but also provided a handle for further selective functionalizations.

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Figures

Scheme 1
Scheme 1
Rautenstrauch 1,2-Acyloxy Migration and Saucy-Marbet 1,3-Acyloxy Migration of Cyclopropyl Propargyl Esters
Scheme 2
Scheme 2
Diverse Products Derived from Transition Metal-Catalyzed Saucy-Marbet 1,3-Acyloxy Migration of Cyclopropyl Substituted Propargyl Esters
Scheme 3
Scheme 3
Proposed Mechanism for the Formation of Alkylidene Cyclohexenone 2a from Cyclopropyl Substituted Propargyl Ester 1a
Scheme 4
Scheme 4
Proposed Mechanism for the Conversion of 1s to 2s
Scheme 5
Scheme 5
Proposed Mechanism for Regioselective Cleavage of C-C σ-Bond of Substituted Cyclopropanes
Scheme 6
Scheme 6
Rh-Catalyzed Ring Expansion of Cyclopropanes in Bicyclic Systems
Scheme 7
Scheme 7
Rh-Catalyzed 1,3-Acyloxy Migration [5+1] Cycloaddition for Substrates 3a and 3b
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References

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