Aluminium-Catalyzed C(sp)-H Borylation of Alkynes.

Angewandte Chemie
Dominic R WillcoxStephen P Thomas

Abstract

Historically used in stoichiometric hydroalumination chemistry, recent advances have transformed aluminium hydrides into versatile catalysts for the hydroboration of unsaturated multiple bonds. This catalytic ability is founded on the defining reactivity of aluminium hydrides with alkynes and alkenes: 1,2-hydroalumination of the unsaturated π-system. This manuscript reports the aluminium hydride catalyzed dehydroborylation of terminal alkynes. A tethered intramolecular amine ligand controls reactivity at the aluminium hydride centre, switching off hydroalumination and instead enabling selective reactions at the alkyne C-H σ-bond. Chemoselective C-H borylation was observed across a series of aryl- and alkyl-substituted alkynes (21 examples). On the basis of kinetic and density functional theory studies, a mechanism in which C-H borylation proceeds by σ-bond metathesis between pinacolborane (HBpin) and alkynyl aluminium intermediates is proposed.

References

Aug 2, 2003·Journal of the American Chemical Society·Aaron D Sadow, T Don Tilley
Jul 4, 2012·Journal of the American Chemical Society·Nicole L DunnAlexander T Radosevich
Jul 13, 2012·Chemistry : a European Journal·Rylan J Lundgren, Mark Stradiotto
Feb 5, 2013·Journal of the American Chemical Society·Chun-I LeeOleg V Ozerov
Jun 8, 2013·Chemical Communications : Chem Comm·Takashi NakazonoKen Sakai
Jul 25, 2013·Nature Chemistry·Konstantin ChernichenkoTimo Repo
Sep 10, 2014·Journal of the American Chemical Society·Weiwei ZiF Dean Toste
Aug 1, 2015·Science·Marc-André LégaréFrédéric-Georges Fontaine
Feb 11, 2016·Journal of the American Chemical Society·Zhi YangHerbert W Roesky
Nov 20, 2016·Angewandte Chemie·Alessandro BismutoMichael J Cowley
Apr 30, 2017·Chemical Science·Erik A RomeroGuy Bertrand
Aug 24, 2017·Chemistry : a European Journal·Shimin ChenHerbert W Roesky
Sep 14, 2017·Journal of the American Chemical Society·Julien Légaré LavergneFrédéric-Georges Fontaine
May 16, 2019·Chemical Society Reviews·Dennis G Hall
May 31, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Yilin ChenHongping Zhu
Jul 10, 2019·Journal of the American Chemical Society·Étienne RochetteFrédéric-Georges Fontaine
Sep 26, 2019·Organic & Biomolecular Chemistry·Taoda ShiWenhao Hu
Nov 21, 2019·Chemical Communications : Chem Comm·Ramkumar KannanAjay Venugopal
Mar 12, 2020·The Journal of Organic Chemistry·Nabin SarkarSharanappa Nembenna

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