generate the 5-membered rhodacycle I. A molecule of CO can
coordinate to the putative rhodacycle to form species II.
Migratory insertion of CO into the Rh-C bond then takes
place to forge the new C–C bond, generating 6-membered
rhodacycle III. At this point reductive elimination can occur to
afford the desired phthalimide and a rhodium(I) species. This
species can undergo two single electron oxidations via Ag2CO3
to render the catalytically active rhodium complex.
In conclusion, we have developed a Rh(III) catalyzed oxidative
carbonylation phthalimide synthesis via C–H/N–H activation. The
reaction utilizes an Rh(III) catalyst in the presence of an Ag(I)
oxidant, and is proposed to proceed by N–H metalation of the
amide followed by ortho C–H activation. The resultant rhodacycle
undergoes CO insertion to form phthalimides in good to excellent
yields. Importantly, in this reaction, the amide substrates and the
coupling partner CO are both fully incorporated into the desired
products.
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We thank the NIGMS for generous support of this research
(GM80442). T.R. thanks Amgen and Roche for unrestricted
support. We thank Johnson Matthey for a generous loan of
Rh salts.
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¨
¨
16 The use of AgOTf as an oxidant affords no desired product. In the
presence of AgOTf and Li2CO3, the desired product is obtained in
23% yield.
3 During the preparation of this manuscript, a related Pd(II)
catalyzed carbonylation of N-alkoxybenzamides was reported.
c
12076 Chem. Commun., 2011, 47, 12074–12076
This journal is The Royal Society of Chemistry 2011