77131-99-8

Upstream product

• 3737-00-6 bromo-3 chloro-1 propene 
• 122-78-1 phenylacetaldehyde 
• 107-05-1 3-chloroprop-1-ene 
• 77131-94-3 3-Chloro-1-phenyl-pent-4-en-2-one 

Relevant academic research and scientific papers

Diastereo- and enantioselective synthesis of syn-α-vinylchlorohydrins and cis-vinylepoxides

A new method to generate chiral syn-vinylchlorohydrins and cis-vinyloxiranes is reported. Reaction of (α-haloallyl)lithiums with methoxy-9-BBN or Ipc2BOMe followed by treatment with BF3·OEt2 leads to (Z)-(γ-haloallyl)boranes which react with aldehydes to yield cis-vinylepoxides (de ≥ 90%) upon oxidative workup. Alternatively, addition of ethanolamine to the allylboration product yields syn-α-halohydrins (de ≥ 90%) that are also easily cyclized to cis-vinylepoxides. Extension of this protocol using [(Z)-γ-chloroallyl]BIpc2 leads to chiral syn-α-chlorohydrins and cis-vinylepoxides in high de (≥90%) and ee (90-99%). Enantioselectivity of reactions of chiral (Z)-(γ-chloroallyl)boranes with aldehydes are more sensitive to reaction conditions than enantioselectivity of reactions of other α-or γ-substituted allylboranes. The effects of proportion of BP3·OEt2 and the relative efficacies of LiNR2 bases on diastereo- and enantioselectivity of the chloroallylation are reported.

HETERO-ATOM SUBSTITUTED CHROMIUM ALLYLS: SYNTHETIC STUDIES ON NEOCARZINOSTATIN CHROMOPHORE ANALOGUES

The preparation and reactions of hetero-atom substituted chromium allyls derived from 7a, 7b, 12, and 15 are described in connection with studies on the synthesis of neocarzinostatin analogues.

Reaction of 3-Chloroallyltrimethylsilane with Acid Chloride and Exploitation of a New Regioselective Synthesis of αβ-Unsaturated Epoxide

α-Chloro-βγ-unsaturated ketone (2) was synthetized from the reaction of 3-chloroallyltrimethylsilane (1) with acid chloride.The ketone was converted into αβ-unsaturated epoxide (3) regioselectively in good yield via reduction with NaBH4 or LiAlH4 followed