title: Chemoselective Coupling of 1,1-Bis[(pinacolato)boryl]alkanes for the Transition-Metal-Free Borylation of Aryl and Vinyl Halides: A Combined Experimental and Theoretical Investigation.
abstract: A new transition-metal-free borylation of aryl and vinyl halides using 1,1-bis[(pinacolato)boryl]alkanes as boron sources is described. In this transformation one of the boron groups from 1,1-bis[(pinacolato)boryl]alkanes is selectively transferred to aryl and vinyl halides in the presence of sodium tert-butoxide as the only activator to form organoboronate esters. Under the developed borylation conditions, a broad range of organohalides are borylated with excellent chemoselectivity and functional group compatibility, thus offering a rare example of a transition-metal-free borylation protocol. Experimental and theoretical studies have been performed to elucidate the reaction mechanism, revealing the unusual formation of Lewis acid/base adduct between organohalides and α-borylcarbanion, generated in situ from the reaction of 1,1-bis[(pinacolato)boryl]alkanes with an alkoxide base, to facilitate the borylation reactions.
authors.affiliation: Department of Chemistry and Division of Advanced Nuclear Engineering, Pohang University of Science and Technology (POSTECH) , Pohang, 37673, Republic of Korea.
authors.forename: Yeosan
authors.initials: Y
authors.lastname: Lee
authors.affiliation: Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST) , Daejeon, 34141, Republic of Korea.|Center for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science (IBS) , Daejeon, 34141, Republic of Korea.
authors.forename: Seung-Yeol
authors.initials: SY
authors.lastname: Baek
authors.affiliation: Department of Chemistry and Division of Advanced Nuclear Engineering, Pohang University of Science and Technology (POSTECH) , Pohang, 37673, Republic of Korea.
authors.forename: Jinyoung
authors.initials: J
authors.lastname: Park
authors.affiliation: Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST) , Daejeon, 34141, Republic of Korea.|Center for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science (IBS) , Daejeon, 34141, Republic of Korea.
authors.forename: Seoung-Tae
authors.identifier: 0000-0003-4067-9567
authors.initials: ST
authors.lastname: Kim
authors.affiliation: Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST) , Daejeon, 34141, Republic of Korea.|Center for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science (IBS) , Daejeon, 34141, Republic of Korea.
authors.forename: Samat
authors.identifier: 0000-0003-3470-1510
authors.initials: S
authors.lastname: Tussupbayev
authors.affiliation: Department of Chemistry and Division of Advanced Nuclear Engineering, Pohang University of Science and Technology (POSTECH) , Pohang, 37673, Republic of Korea.
authors.forename: Jeongho
authors.initials: J
authors.lastname: Kim
authors.affiliation: Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST) , Daejeon, 34141, Republic of Korea.|Center for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science (IBS) , Daejeon, 34141, Republic of Korea.
authors.forename: Mu-Hyun
authors.initials: MH
authors.lastname: Baik
authors.affiliation: Department of Chemistry and Division of Advanced Nuclear Engineering, Pohang University of Science and Technology (POSTECH) , Pohang, 37673, Republic of Korea.
authors.forename: Seung Hwan
authors.identifier: 0000-0001-5803-4922
authors.initials: SH
authors.lastname: Cho