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Complementary regioselectivity in the Cu(I)-catalyzed diamination of conjugated dienes to form cyclic sulfamides.

ABSTRACT: This paper describes the regioselective diamination of conjugated dienes using inexpensive Cu(I) as catalyst and N,N-di-tert-butylthiadiaziridine 1,1-dioxide as nitrogen source. The regioselectivity of diamination is likely due to dual mechanistic pathways which are greatly influenced by reaction conditions and the nature of the diene. A variety of useful internal and terminal cyclic sulfamides can be obtained in good yield.

SUBMITTER: Cornwall RG

PROVIDER: S-EPMC3031742 | biostudies-literature | 2011 Feb

REPOSITORIES: biostudies-literature

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Complementary regioselectivity in the Cu(I)-catalyzed diamination of conjugated dienes to form cyclic sulfamides.

Cornwall Richard G RG Zhao Baoguo B Shi Yian Y

Organic letters 20101230 3

This paper describes the regioselective diamination of conjugated dienes using inexpensive Cu(I) as catalyst and N,N-di-tert-butylthiadiaziridine 1,1-dioxide as nitrogen source. The regioselectivity of diamination is likely due to dual mechanistic pathways which are greatly influenced by reaction conditions and the nature of the diene. A variety of useful internal and terminal cyclic sulfamides can be obtained in good yield. ...[more]

PMID: 21192669

Similar Datasets

Cu(I)-catalyzed diamination of conjugated dienes. Complementary regioselectivity from two distinct mechanistic pathways involving Cu(II) and Cu(III) species.

Project description:Conjugated dienes can be diaminated at the internal and/or terminal double bonds using Cu(I) as catalyst and N,N-di-t-butyldiaziridinone (1) as nitrogen source. The regioselectivity is highly dependent upon the choice of Cu(I) catalyst and the substituents on diene substrates. The diamination likely proceeds via two mechanistically distinct pathways. The N-N bond of N,N-di-t-butyldiaziridinone (1) is first homolytically cleaved by the Cu(I) catalyst to form four-membered Cu(III) species A and Cu(II) radical species B, which are in rapid equilibrium. The internal diamination likely proceeds in a concerted manner via Cu(III) species A, and the terminal diamination likely involves Cu(II) radical species B. Kinetic studies have shown that the diamination is first-order in N,N-di-t-butyldiaziridinone (1), zero-order in olefin, and first-order in total Cu(I) catalyst, and the cleavage of the N-N bond of 1 by the Cu(I) catalyst is the rate-determining step. The internal diamination is favored by use of CuBr without ligand and electron-rich dienes. The terminal diamination is favored when using CuCl-L and dienes with radical-stabilizing groups.

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Cu(I)-catalyzed regioselective diamination of conjugated dienes via dual mechanistic pathways.

Project description:This paper describes the Cu(I)-catalyzed regioselective diamination of conjugated dienes using di-tert-butyldiaziridinone as nitrogen source. The internal diamination and terminal diamination likely proceed via two mechanistic pathways. Various dienes can be efficiently diaminated at the internal double bonds with high regio- and diasteroselectivity in good yield using inexpensive CuBr as catalyst.

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Ni(0)-catalyzed 1,4-selective diboration of conjugated dienes.

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