Alkynes as Allylmetal Equivalents in Redox-Triggered C–C Couplings to Primary Alcohols: (Z)-Homoallylic Alcohols via Ruthenium-Catalyzed Propargyl C–H Oxidative Addition

[Image: see text] The cationic ruthenium catalyst generated upon the acid–base reaction of H(2)Ru(CO)(PPh(3))(3) and 2,4,6-(2-Pr)(3)PhSO(3)H promotes the redox-triggered C–C coupling of 2-alkynes and primary alcohols to form (Z)-homoallylic alcohols with good to complete control of olefin geometry....

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Autores principales: Park, Boyoung Y., Nguyen, Khoa D., Chaulagain, Mani Raj, Komanduri, Venukrishnan, Krische, Michael J.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2014
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4151781/
https://www.ncbi.nlm.nih.gov/pubmed/25075434
http://dx.doi.org/10.1021/ja505962w
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author Park, Boyoung Y.
Nguyen, Khoa D.
Chaulagain, Mani Raj
Komanduri, Venukrishnan
Krische, Michael J.
author_facet Park, Boyoung Y.
Nguyen, Khoa D.
Chaulagain, Mani Raj
Komanduri, Venukrishnan
Krische, Michael J.
author_sort Park, Boyoung Y.
collection PubMed
description [Image: see text] The cationic ruthenium catalyst generated upon the acid–base reaction of H(2)Ru(CO)(PPh(3))(3) and 2,4,6-(2-Pr)(3)PhSO(3)H promotes the redox-triggered C–C coupling of 2-alkynes and primary alcohols to form (Z)-homoallylic alcohols with good to complete control of olefin geometry. Deuterium labeling studies, which reveal roughly equal isotopic compositions at the allylic and distal vinylic positions, along with other data, corroborate a catalytic mechanism involving ruthenium(0)-mediated allene–aldehyde oxidative coupling to form a transient oxaruthenacycle, an event that ultimately defines (Z)-olefin stereochemistry.
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spelling pubmed-41517812015-07-30 Alkynes as Allylmetal Equivalents in Redox-Triggered C–C Couplings to Primary Alcohols: (Z)-Homoallylic Alcohols via Ruthenium-Catalyzed Propargyl C–H Oxidative Addition Park, Boyoung Y. Nguyen, Khoa D. Chaulagain, Mani Raj Komanduri, Venukrishnan Krische, Michael J. J Am Chem Soc [Image: see text] The cationic ruthenium catalyst generated upon the acid–base reaction of H(2)Ru(CO)(PPh(3))(3) and 2,4,6-(2-Pr)(3)PhSO(3)H promotes the redox-triggered C–C coupling of 2-alkynes and primary alcohols to form (Z)-homoallylic alcohols with good to complete control of olefin geometry. Deuterium labeling studies, which reveal roughly equal isotopic compositions at the allylic and distal vinylic positions, along with other data, corroborate a catalytic mechanism involving ruthenium(0)-mediated allene–aldehyde oxidative coupling to form a transient oxaruthenacycle, an event that ultimately defines (Z)-olefin stereochemistry. American Chemical Society 2014-07-30 2014-08-27 /pmc/articles/PMC4151781/ /pubmed/25075434 http://dx.doi.org/10.1021/ja505962w Text en Copyright © 2014 American Chemical Society Terms of Use (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html)
spellingShingle Park, Boyoung Y.
Nguyen, Khoa D.
Chaulagain, Mani Raj
Komanduri, Venukrishnan
Krische, Michael J.
Alkynes as Allylmetal Equivalents in Redox-Triggered C–C Couplings to Primary Alcohols: (Z)-Homoallylic Alcohols via Ruthenium-Catalyzed Propargyl C–H Oxidative Addition
title Alkynes as Allylmetal Equivalents in Redox-Triggered C–C Couplings to Primary Alcohols: (Z)-Homoallylic Alcohols via Ruthenium-Catalyzed Propargyl C–H Oxidative Addition
title_full Alkynes as Allylmetal Equivalents in Redox-Triggered C–C Couplings to Primary Alcohols: (Z)-Homoallylic Alcohols via Ruthenium-Catalyzed Propargyl C–H Oxidative Addition
title_fullStr Alkynes as Allylmetal Equivalents in Redox-Triggered C–C Couplings to Primary Alcohols: (Z)-Homoallylic Alcohols via Ruthenium-Catalyzed Propargyl C–H Oxidative Addition
title_full_unstemmed Alkynes as Allylmetal Equivalents in Redox-Triggered C–C Couplings to Primary Alcohols: (Z)-Homoallylic Alcohols via Ruthenium-Catalyzed Propargyl C–H Oxidative Addition
title_short Alkynes as Allylmetal Equivalents in Redox-Triggered C–C Couplings to Primary Alcohols: (Z)-Homoallylic Alcohols via Ruthenium-Catalyzed Propargyl C–H Oxidative Addition
title_sort alkynes as allylmetal equivalents in redox-triggered c–c couplings to primary alcohols: (z)-homoallylic alcohols via ruthenium-catalyzed propargyl c–h oxidative addition
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4151781/
https://www.ncbi.nlm.nih.gov/pubmed/25075434
http://dx.doi.org/10.1021/ja505962w
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