H. Reich, M. Schroeder, I. Reich
1984
Citations
0
Influential Citations
9
Citations
Journal
Israel Journal of Chemistry
Abstract
Metalation of methallyl phenyl selenide, allyl phenyl selenide, and methallyl phenyl sulfide followed by tri-n-butylstannylation gave exclusively the γ-stannylated sulfide or selenide (e.g., 1-phenylseleno-2-methyl-3-tri-n-butylstannyl-1-propene (5)). Compound 5 reacts with a series of immonium electrophiles to give products of aminomethylation α- to selenium. Electrophiles have included N-(bromomethyl)phthalimide/ZnBr2, Eschenmoser salt (dimethylmethyleneammonium iodide), and Mannich reagents generated in situ from diethylamine, piperidine, isopropyl sarcosinate and benzylmethylamine. The selenide from the last of these amines (N, 3-dimethyl-N-benzyl-2-phenylseleno-3-butenamine, 10) has been subjected to further transformations as follows: (1) treatment of 10 with trimethylstannyllithium results in replacement of phenylseleno by stannyl; this allyltin (11) can then again be aminomethylated giving compound 12 or 13; (2) oxidation of 10 gives amino alcohol 14 by [2, 3] sigmatropic rearrangement of the allyl selenoxide; (3) photolysis of 10 results in 1,3-rearrangement of the phenylseleno group; oxidative rearrangement of this allyl selenide gives amino alcohol 16. The phthalimidomethylation product (6) is converted to a precursor for the side chain of the cytokinin zeatin by oxidation and [2, 3] sigmatropic rearrangement.