We have reported Rh-catalyzed CO-retentive addition of acid chlorides to terminal alkynes,which affords beta-chlorovinyl ketones,a useful class of synthetic intermediates.In these reactions,electron-withdrawing groups like fluorine are required in starting materials to avoid decarbonylation.Since the C-F bond is stable,however,it is not easy to synthetically manipulate the fluorinated acyl or aroyl group in the product,except for the transformation at the carbonyl group.Our continued study has uncovered that chloroacetyl chloride also adds to alkynes to furnish (Z)-1,4-dichloro-3-buten-2-ones (Scheme 1),which allow numerous synthetic manipulation of the resulting Cl-C bonds.
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