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Organoselenium Chemistry. Preparation of Allyl and Homoallyl Amines by Aminomethylation of Phenylseleno‐Substituted Allyl Tin Reagents
Author(s) -
Reich Hans J.,
Schroeder Mel C.,
Reich Ieva L.
Publication year - 1984
Publication title -
israel journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.908
H-Index - 54
eISSN - 1869-5868
pISSN - 0021-2148
DOI - 10.1002/ijch.198400027
Subject(s) - chemistry , selenide , medicinal chemistry , stannane , electrophile , allyl alcohol , organic chemistry , selenium , catalysis
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/ZnBr 2 , 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.