Cycloalkanes bridged

R. A. Alonso, G. D. Vile, R. E. McDevitt, and B. Fraser-Reid, Radical cyclization routes to bridged pyranosides as precursors of densely functionalized cycloalkanes, J. Org. Chem. 57 573 (1992). 

Metal nitrene complexes were used in a number of C-H amination reactions (recent reviews [358, 359]). Copper ketiminate complexes react with azides to nitrene complexes, which were isolated [360]. (p-Ketiminate)copper(I) complex 262 (2.5 mol%) serves therefore as an efficient catalyst for the intermolecular C-H amination of alkylarenes, cycloalkanes, or benzaldehydes 260 using adamantyl azide 261 as the nitrogen source ig. 68) [361]. The corresponding adamantyl amines or amides 263 were isolated in 80-93% yield. Copper complex 262 forms initially a dinuclear bridged complex with 261. From this a copper nitrene complex is generated by elimination of nitrogen, which mediates the hydrogen abstraction from 260. 

One advantage of this approach is that we plan to assemble 60 in a modular fashion (Scheme 18). By systematically varying the pendant arene, the cycloalkane with its substituents, and the group that bridges the two carboxylates, we should be able prepare a combinatorial family of catalysts. 

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