ISSN:
0018-019X
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Nucleophilic substitution of 6β-chloro-7,8-didehydro-4,5α-epoxy-3-methoxy-17-methylmorphinan (1) and 8α-bromo-6,7-didehydro-4,5α-epoxy-3-methoxy-17-methylmorphinan (2) with lithium cyano(methyl)- and (aryl)cyanocuprates(I) (5a-c) was accompanied by allylic rearrangement with both change and retention of orientation of the substituting group (Scheme 1, Table 1). Nucleophilic substitution in 7,8-didehydro-4,5α-epoxy-3-methoxy-17-methylmorphinan-6α-yl methanesulfonate (3) and 7,8-didehydro-4,5α-epoxy-3-methoxy-17-methylmorphinan-6β-yl methanesulfonate (4) proceeded without allylic rearrangement with both change and retention of the orientation of the substituting group (Scheme 2, Table 1). X-Ray diffraction studies of the products 6,7-didehydro-4,5α-epoxy-3-methoxy-17-methyl-8α-phenylmorphinan (6b) and 7,8-didehydro-4,5α-epoxy-3-methoxy-17-methyl-6β-phenylmorphinan (7b) were carried out (Figs. 1 and 2).
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/hlca.19940770119
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