Synfacts 2005(1): 0110-0110  
DOI: 10.1055/s-2005-872201
Synthesis of Heterocycles
© Georg Thieme Verlag Stuttgart · New York

Synthesis of a Highly Strained Heterocycle Involving a Nitro Acetal to Aminal Rearrangement

Contributor(s): Victor Snieckus, Oleg M. Demchuk
S. E. Denmark*, J. I. Montgomery
University of Illinois, Urbana, USA
Further Information

Publication History

Publication Date:
21 September 2005 (online)

Significance

The highly strained [5.5.5.4]-1-azafenestrane was efficiently prepared using tandem [4+2], [3+2] cycloadditions of nitroalkene as the key step, 2 to 1. A bonus uncovered in the route towards the target molecule involved a dyotropic rearrangement of a nitro acetal into a tetracyclic aminal, 3 to 4. X-ray structure crystallographic analysis of the azafenestrane indicates significant planarized distortion [N1-C1-C7 119.8(7)° and C4-C1-C10 120.7(8)°] of the central carbon atom. The degree of distortion agrees well with calculated values for the corresponding parent hydrocarbon (M. Thommen, R. Keese Synlett 1997, 231-240).