Herein,
we describe the first oxysilylation of unsaturated carboxylic
acids mediated by di-tert-butyl peroxide (DTBP),
which enables the rapid and efficient preparation of silyl lactone
compounds. This process tolerates functional groups, such as methyl,
methoxy, halogen (fluoride and chloride), and cyano moieties. Furthermore,
the strategy allows the application of a wide range of primary, secondary,
and tertiary hydrosilanes for functionalization.
A chemoselective silylation of terminal alkynes with trifluoromethyltrialkylsilane in 1,3‐dimethyl‐3,4,5,6‐tetrahydro‐2(1H)‐pyrimidinone (DMPU) is described. This process is effective even under mild conditions without the use of fluorides or an N‐heterocyclic carbene (NHC), providing a widely applicable method for the synthesis of alkynylsilicon compounds. Moreover, it was found that the preferential deprotonation of terminal alkynes using this system proceeded faster than the trifluoromethylation of aldehydes, ketones, and esters.
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