Terminal Alkyne Coupling Reactions through a Ring: Mechanistic Insights and Regiochemical Switching

Angewandte Chemie
Caroline M StoreyAdrian B Chaplin

Abstract

The mechanism and selectivity of terminal alkyne coupling reactions promoted by rhodium(I) complexes of NHC-based CNC pincer ligands have been investigated. Synthetic and kinetic experiments support E- and gem-enyne formation through a common reaction sequence involving hydrometallation and rate-determining C-C bond reductive elimination. The latter is significantly affected by the ligand topology: Employment of a macrocyclic variant enforced exclusive head-to-head coupling, contrasting the high selectivity for head-to-tail coupling observed for the corresponding acyclic pincer ligand.

References

Nov 17, 2001·Chemical Reviews·B M TrostA B Pinkerton
Dec 24, 2005·Chemical Communications : Chem Comm·Wei WengOleg V Ozerov
Jul 18, 2008·Chemical Communications : Chem Comm·Takashi KatagiriMasahiro Miura
Jul 10, 2009·Chemical Society Reviews·James D CrowleyRoy T McBurney
Aug 15, 2009·Chemical Reviews·Jianzhao LiuBen Zhong Tang
Nov 2, 2011·Chemical Reviews·Léo LeroyerRemi Chauvin
Oct 12, 2013·Chemistry : a European Journal·Laura Rubio-PérezLuis A Oro
Nov 10, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Rhiann E Andrew, Adrian B Chaplin
Jan 11, 2014·Inorganic Chemistry·Joaquín AlósMarta Valencia
Dec 11, 2014·Inorganic Chemistry·Rhiann E Andrew, Adrian B Chaplin
Feb 4, 2016·Chemical Communications : Chem Comm·George KleinhansDaniela I Bezuidenhout
Apr 19, 2016·Chemical Society Reviews·Barry M Trost, James T Masters
Apr 22, 2016·Angewandte Chemie·Orestes Rivada-WheelaghanDavid Milstein
May 10, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Rhiann E AndrewAdrian B Chaplin
Jun 14, 2016·Organic & Biomolecular Chemistry·Yujing ZhouJianbo Wang
Apr 28, 2017·Chemical Society Reviews·James E M LewisStephen M Goldup
Feb 13, 2018·Chemical Society Reviews·Eduardo Peris, Robert H Crabtree

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Citations

Sep 13, 2018·Chemistry : a European Journal·Ana M GeerCristina Tejel
Dec 12, 2019·Chemistry, an Asian Journal·Koji YamamotoToshikazu Takata
Feb 8, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Baptiste LeforestierAdrian B Chaplin
Jan 9, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Thomas M HoodAdrian B Chaplin
May 7, 2020·Chemistry : a European Journal·María Galiana-CameoRicardo Castarlenas
Feb 8, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Matthew R GytonAdrian B Chaplin
Jul 18, 2020·Chemistry : a European Journal·Caroline M StoreyAdrian B Chaplin
Sep 16, 2020·Angewandte Chemie·Baptiste LeforestierAdrian B Chaplin
Nov 12, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Thomas M Hood, Adrian B Chaplin
Dec 18, 2020·European Journal of Inorganic Chemistry·Amy E KynmanAdrian B Chaplin
Jan 30, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Thomas M Hood, Adrian B Chaplin
Apr 4, 2021·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Ronja Jordan, Doris Kunz
Apr 19, 2019·Organic Letters·Louis Jeanne-JulienEmmanuel Roulland

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Methods Mentioned

BETA
NMR

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