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. 2016;7(12):6934-6939.
doi: 10.1039/C6SC02231F. Epub 2016 Jul 28.

Intramolecular 1,5-C(sp3)-H Radical Amination via Co(II)-Based Metalloradical Catalysis for Five-Membered Cyclic Sulfamides

Hongjian Lu  1 , Kai Lang  2 , Huiling Jiang  3 , Lukasz Wojtas  3 , X Peter Zhang  2
Affiliations

Intramolecular 1,5-C(sp3)-H Radical Amination via Co(II)-Based Metalloradical Catalysis for Five-Membered Cyclic Sulfamides

Hongjian Lu et al. Chem Sci. 2016.

Abstract

Co(II)-based metalloradical catalysis (MRC) proves effective for intramolecular 1,5-C-H amination of sulfamoyl azides under neutral and nonoxidative conditions, providing a straightforward approach to access strained 5-membered cyclic sulfamides with nitrogen gas as the only byproduct. The metalloradical amination system is applicable to different types of C(sp3)-H bonds and has a high degree of functional group tolerance. Additional features of the Co(II)-catalyzed 1,5-C-H amination include excellent chemoselectivity toward allylic and propargylic C-H bonds. The unique reactivity and selectivity profile of the Co(II)-catalyzed 1,5-C-H amination is attributed to the underlying radical mechanism of MRC.

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Figures

Scheme 1
Scheme 1. Metalloradical approach for 5-membered cyclic sulfamides via radical C(sp3)–H amination.
Fig. 1
Fig. 1. Selected examples of biologically active molecules containing the 5-membered cyclic sulfamide motif.
Scheme 2
Scheme 2. Ligand effect on Co(ii)-catalyzed 1,5-C(sp3)–H metalloradical amination.
Scheme 3
Scheme 3. Late-stage functionalization of complex molecules by Co(ii)- based 1,5-C–H radical aminationa. (a) Isolated yields. (b) On 0.5 mmol scale.
Fig. 2
Fig. 2. (A) Comparison of geometric parameters between acyclic and cyclic sulfamides based on X-ray structures. (B) Geometries of proposed transitional states for stepwise (left) and concerted (right) processes of intramolecular 1,5-C(sp3)–H amination.
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