Generation of azines by the reaction of a nucleophilic carbene with diazoalkanes: a synthetic and crystallographic study

J M Hopkins; M Bowdridge; K N Robertson; T S Cameron; H A Jenkins; J A Clyburne

doi:10.1021/jo001515b

Generation of azines by the reaction of a nucleophilic carbene with diazoalkanes: a synthetic and crystallographic study

J Org Chem. 2001 Aug 24;66(17):5713-6. doi: 10.1021/jo001515b.

Authors

J M Hopkins¹, M Bowdridge, K N Robertson, T S Cameron, H A Jenkins, J A Clyburne

Affiliation

¹ Department of Chemistry, Acadia University, Wolfville, Nova Scotia, B0P 1X0, Canada.

PMID: 11511243
DOI: 10.1021/jo001515b

Abstract

Reactions of the nucleophilic carbene 1,3-dimesityl-imidazol-2-ylidene (1) with diazofluorene, diphenyldiazomethane, and azidotrimethylsilane were examined. Specifically, carbene 1 reacts with diazofluorene and diphenyldiazomethane to give addition products (azines: 3 and 4, respectively). Compounds 3 and 4 were further characterized in the solid-state by single-crystal X-ray crystallographic studies. [3 (a = 9.7936(6) A, b = 10.0529(7) A, c = 16.251(1) A, alpha = 75.765(1) degrees, beta = 79.711(1) degrees, gamma = 64.321(1) degrees, Z = 2, space group P1); 4 (a = 11.681(3) A, b = 11.861(4) A, c = 21.186(3) A, alpha = 90 degrees, beta = 97.05(2) degrees, gamma = 90 degrees, Z = 4, space group P2(1)/n)]. The structural parameters of 3 and 4 are discussed with reference to previously characterized symmetrical and unsymmetrical azines. Structural data suggest that charge separation is possible in 3.