Imine Allylations by Allylic Trichlorotins Derived from α,α-Diisopropylhomoallylic Alcohols with Tin(II) Chloride and N-Chlorosuccinimide

Yoshiro  Masuyama; Naoko  Yamamoto; Yasuhiko  Kurusu

doi:10.1055/s-2002-35581

LETTER

Imine Allylations by Allylic Trichlorotins Derived from α,α-Diisopropylhomoallylic Alcohols with Tin(II) Chloride and N-Chlorosuccinimide

Yoshiro Masuyama*, Naoko Yamamoto, Yasuhiko Kurusu
Department of Chemistry, Faculty of Science and Technology, Sophia University, 7-1 Kioicho, Chiyoda-ku, Tokyo 102-8554, Japan
Fax: +81(3)32383361; e-Mail: y-masuya@sophia.ac.jp;

Abstract

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Abstract

Allylic trichlorotins, prepared in situ from α,α-diisopropylhomoallylic alcohols with tin(II) chloride and N-chlorosuccinimide in dichloromethane at -40 ºC, cause nucleophilic addition to N-tosylimines or N-tosyliminiums to afford the corresponding α-substituted homoallylic amines.

Key words

nucleophilic additions - allylations - organometallic reagents - allylic tins - homoallylic amines

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References

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The syn-diastereoselectivity in the allylations by 5 was confirmed by the comparison of ¹H NMR spectra with authentic samples prepared by the imine allylation by 1-bromo-2-butene with indium. [3] In addition the diastereo-selectivity in ref. [9] has been mistaken; syn adducts are major, similarly to the imine allylation by 5.

The E:Z ratio of A could not be determined by the ¹H NMR observation of the reaction of 5 with SnCl₂ and NCS in CD₂Cl₂ either at -40 ºC or at room temperature. Since the E:Z ratios of α-adducts in the carbonyl allylation by 5 are ca. 1:1 to 1:4, [8] the 2-butenyltrichlorotin intermediate is presumed to be an E,Z mixture.