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. 2009;48(15):2777-9.
doi: 10.1002/anie.200806192.

Synthesis of 1,3-diamines through rhodium-catalyzed C-H insertion

Toshiki Kurokawa  1 , Mihyong Kim, J Du Bois
Affiliations

Synthesis of 1,3-diamines through rhodium-catalyzed C-H insertion

Toshiki Kurokawa et al. Angew Chem Int Ed Engl. 2009.

Abstract

A grand opening: N-Boc-N-alkylsulfamides are effective substrates for the title transformation. Oxidative cyclization is highly chemoselective as well as being both stereospecific and diastereoselective. With the advent of new protocols that facilitate ring opening of the six-membered-ring heterocyclic products, access to differentially protected 1,3-diamines has been made possible (see scheme).

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Figures

Scheme 1
Scheme 1
A C—H amination strategy for the synthesis of cyclic sulfamides and 1,3-diamines. Boc = tert-butoxycarbonyl.
Scheme 2
Scheme 2
Two preparative methods for the assembly of N-Boc-N-alkylsulfamides. CBz=benzyloxycarbonyl.
Scheme 3
Scheme 3
A proposed stereochemical model for C—H insertion.
Scheme 4
Scheme 4
Facile ring-opening reactions to afford protected 1,3-diamines.
Scheme 5
Scheme 5
An alternative ring-opening sequence. DMAP = 4-dimethyl-aminopyridine.
See this image and copyright information in PMC

References

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    1. One example of an intramolecular alkylsulfamide C—H insertion reaction was shown in a prior report, see: Espino CG, Fiori KW, Kim M, Du Bois J. J. Am. Chem. Soc. 2004;126:15378–15379.

    1. For metal-catalyzed diamination of alkenes using sulfamides, see: Muñiz K, Streuff J, Hövelmann CH, Núñez A. Angew. Chem. 2007;119:7255–7258. Angew. Chem. Int. Ed. 2007, 46, 7125–7127. Zabawa TP, Kasi D, Chemler SR. J. Am. Chem. Soc. 2005;127:11250–11251.

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