Highly selective catalytic trans -hydroboration of alkynes mediated by borenium cations and B(C6 F5 )3

Chemical Science
John S McGoughMichael J Ingleson

Abstract

The trans-hydroboration of terminal alkynes mediated by borenium cations [NHC(9-BBN)]+ (NHC = N-heterocyclic carbene, 9-BBN = 9-borabicyclo(3.3.1)nonane) exclusively affords Z-vinylboranes. NHCs and chelating dialkyl substituents on the borenium cation and "non"-basic anions were essential to preclude alternative reactions including dehydroboration. Deuterium labelling studies indicate the mechanism involves addition of the boron electrophile to the alkyne and transfer of hydride to the opposite face of the activated alkyne. trans-Hydroboration proceeds with only catalytic amounts of B(C6F5)3 or [Ph3C][B(C6F5)4] to activate the (NHC)9-BBN(H) precursor with the borenium regenerated in the hydride transfer step. The NHC can be removed from the trans-hydroborated products by the addition of Et2O-BF3 providing access to vinylBBN species effective for Suzuki-Miyaura couplings to generate Z-alkenes. Combinations of catalytic B(C6F5)3 and stoichiometric [HB(C6F5)3]- also lead to trans-hydroboration of terminal alkynes to form Z-isomers of [arylCH[double bond, length as m-dash]CHB(C6F5)3]-.

References

Nov 1, 1996·The Journal of Organic Chemistry·Naoki AsaoYoshinori Yamamoto
Jan 5, 2002·The Journal of Organic Chemistry·Min Shi, Bo Xu
Mar 16, 2002·The Journal of Organic Chemistry·Michael RubinVladimir Gevorgyan
Aug 9, 2005·Angewandte Chemie·Warren E PiersKorey D Conroy
Jun 3, 2009·Journal of the American Chemical Society·Meghan A Dureen, Douglas W Stephan
Jan 29, 2010·Chemical Communications : Chem Comm·Hervé Clavier, Steven P Nolan
Nov 26, 2011·Chemical Communications : Chem Comm·Gerald Kehr, Gerhard Erker
Apr 24, 2012·Chemical Reviews·Timothy S De VriesEdwin Vedejs
Jun 21, 2012·Journal of the American Chemical Society·Aleksandrs ProkofjevsEdwin Vedejs
Aug 24, 2012·Journal of the American Chemical Society·Chidambaram GunanathanWalter Leitner
Aug 31, 2012·Journal of the American Chemical Society·Jeffrey M FarrellDouglas W Stephan
Oct 4, 2012·Journal of the American Chemical Society·Patrick EisenbergerCathleen M Crudden
Aug 29, 2013·Journal of the American Chemical Society·Xiangcheng PanDennis P Curran
Oct 4, 2013·Journal of the American Chemical Society·Aleksandrs ProkofjevsEdwin Vedejs
Oct 5, 2013·Chemical Society Reviews·Alastair J J Lennox, Guy C Lloyd-Jones
Nov 1, 2013·Angewandte Chemie·Basker Sundararaju, Alois Fürstner
Nov 22, 2013·Journal of the American Chemical Society·Manuel PérezDouglas W Stephan
Jul 18, 2014·Journal of the American Chemical Society·Kazunori NagaoMasaya Sawamura
Aug 21, 2014·Chemistry : a European Journal·Ian A Cade, Michael J Ingleson
Apr 18, 2015·Journal of the American Chemical Society·Jennifer V ObligacionPaul J Chirik
Aug 1, 2015·Science·Marc-André LégaréFrédéric-Georges Fontaine
Sep 17, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·James R LawsonMichael J Ingleson
Jan 1, 2016·Chemical Science·Gerald Kehr, Gerhard Erker

❮ Previous
Next ❯

Citations

Aug 11, 2018·Chemistry : a European Journal·Hauke KelchHolger Braunschweig
Nov 15, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Práxedes SánchezAndrés Suárez
Nov 20, 2018·Chemical Communications : Chem Comm·Souvik MandalK Geetharani
Dec 12, 2018·Chemical Communications : Chem Comm·Jamie L CardenRebecca L Melen
Jun 13, 2019·Chemistry : a European Journal·Lauren E Longobardi, Alois Fürstner
Jul 18, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Long WangGerhard Erker
Jul 25, 2019·Chemistry, an Asian Journal·Souvik MandalK Geetharani
Sep 12, 2019·Chemical Communications : Chem Comm·Milan Kumar BisaiSakya S Sen
Feb 27, 2020·Chemical Society Reviews·Jamie L CardenRebecca L Melen
Dec 13, 2016·Science·Douglas W Stephan
Mar 16, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·P Eisenberger, C M Crudden
Oct 19, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·James R LawsonRebecca L Melen
Jul 26, 2017·Philosophical Transactions. Series A, Mathematical, Physical, and Engineering Sciences·Jennifer MörickeGerhard Erker
Jul 8, 2017·Chemistry : a European Journal·James R LawsonRebecca L Melen
Aug 12, 2017·Chemistry : a European Journal·Stephen J GeierStephen A Westcott
Mar 10, 2018·Chemistry : a European Journal·Niklas ZwettlerNadia C Mösch-Zanetti
Apr 13, 2017·Chemical Record : an Official Publication of the Chemical Society of Japan ... [et Al.]·Gerald Kehr, Gerhard Erker
May 14, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Louie Fan, Douglas W Stephan
Jun 29, 2016·Chemical Communications : Chem Comm·Marc DevillardDidier Bourissou
Jul 19, 2016·Chemical Communications : Chem Comm·Mirco FleigeDouglas W Stephan
Jul 6, 2016·Chemistry : a European Journal·Lauren E LongobardiDouglas W Stephan
Jun 14, 2017·Angewandte Chemie·Valerio FasanoMichael J Ingleson
Jul 8, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Jolie LamDouglas W Stephan
Mar 3, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Shunxi DongGerhard Erker
May 31, 2018·Angewandte Chemie·Masaki ShimoiTsuyoshi Taniguchi
May 10, 2017·Chemistry : a European Journal·John S McGoughMichael J Ingleson
Jul 26, 2017·Philosophical Transactions. Series A, Mathematical, Physical, and Engineering Sciences·Lewis C WilkinsRebecca L Melen
Feb 12, 2017·Angewandte Chemie·Thorsten ScherpfViktoria H Gessner
Dec 13, 2017·Chemical Communications : Chem Comm·Fu An Tsao, Douglas W Stephan
Dec 21, 2016·Angewandte Chemie·Miguel F Silva ValverdeMatthias Tamm
Jun 18, 2021·The Journal of Organic Chemistry·Nhan N H TonThanh Vinh Nguyen
Oct 28, 2019·Journal of the American Chemical Society·Eduardo Nieto-SepulvedaGuy C Lloyd-Jones
Sep 17, 2019·Journal of the American Chemical Society·Kensuke YamamotoShinichi Saito
Jul 16, 2020·Journal of the American Chemical Society·Qiang FengJianwei Sun
Feb 6, 2017·Inorganic Chemistry·James R Lawson, Rebecca L Melen
Mar 24, 2016·Journal of the American Chemical Society·Konstantin ChernichenkoTimo Repo
Jun 27, 2017·The Journal of Organic Chemistry·Carlotta FigliolaAlison Thompson
Jul 4, 2018·Chemical Reviews·Vitaly NesterovShigeyoshi Inoue

❮ Previous
Next ❯

Methods Mentioned

BETA
NMR
column chromatography
X-ray

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.

Related Papers

Journal of the American Chemical Society
Chidambaram GunanathanWalter Leitner
Dalton Transactions : an International Journal of Inorganic Chemistry
J J ClarkeC M Crudden
© 2022 Meta ULC. All rights reserved