244. Guide to enantioselective dirhodium(II)-catalyzed cyclopropanation with aryldiazoacetates

Authors: Kathryn M. Chepiga, Changming Qin, Joshua S. Alford, Spandan Chennamadhavuni, Timothy M. Gregg, Jeremy P. Olson, Huw M.L. Davies


20136927-28, 5765–5771


Catalytic enantioselective methods for the generation of cyclopropanes have been of long standing pharmaceutical interest. Chiral dirhodium(II) catalysts prove to be an effective means for the generation of diverse cyclopropane libraries. Rh2(R-DOSP)4 is generally the most effective catalyst for asymmetric intermolecular cyclopropanation of methyl aryldiazoacetates with styrene. Rh2(S-PTAD)4 provides high levels of enantioinduction with ortho-substituted aryldiazoacetates. The less-established Rh2(R-BNP)4 plays a complementary role to Rh2(R-DOSP)4 and Rh2(S-PTAD)4 in catalyzing highly enantioselective cyclopropanation of 3-methoxy substituted aryldiazoacetates. Substitution on the styrene has only moderate influence on the asymmetric induction of the cyclopropanation.

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