Utility of the protocol was illustrated by functionalization of naturally occurring ketones, namely, camphor and estrone, that were transformed into alkenyl boronates 2s and 2t (used without characterization) through the boron-Wittig olefination with bis[(pinacolato)boryl]methane. Target fluorinated derivatives 4s and 4t were obtained in 2-3 steps in 31% and 33% overall yield based on the corresponding natural compound, respectively. Reaction of -ethoxyvinyl boronate 2u (E:Z = 35:65) produced corresponding product 4u; however, its isolation in pure form by fractional distillation failed due to close boiling points of the contaminants. To overcome this issue, t-Bu ester 4u was prepared using tert-butyl bromodifluoroacetate as the starting material and isolated successfully by fractional distillation. Considering the reaction stereoselectivity, compound 4u was obtained as a 20:80 mixture of Eand Z-isomers.