trans-Diastereoselective Ru(II)-Catalyzed Asymmetric Transfer Hydrogenation of α-Acetamido Benzocyclic Ketones via Dynamic Kinetic Resolution

[Image: see text] A highly efficient enantio- and diastereoselective catalyzed asymmetric transfer hydrogenation via dynamic kinetic resolution (DKR–ATH) of α,β-dehydro-α-acetamido and α-acetamido benzocyclic ketones to ent-trans-β-amido alcohols is disclosed employing a new ansa-Ru(II) complex of a...

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Autores principales: Cotman, Andrej Emanuel, Lozinšek, Matic, Wang, Baifan, Stephan, Michel, Mohar, Barbara
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2019
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6750876/
https://www.ncbi.nlm.nih.gov/pubmed/31058516
http://dx.doi.org/10.1021/acs.orglett.9b01069
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author Cotman, Andrej Emanuel
Lozinšek, Matic
Wang, Baifan
Stephan, Michel
Mohar, Barbara
author_facet Cotman, Andrej Emanuel
Lozinšek, Matic
Wang, Baifan
Stephan, Michel
Mohar, Barbara
author_sort Cotman, Andrej Emanuel
collection PubMed
description [Image: see text] A highly efficient enantio- and diastereoselective catalyzed asymmetric transfer hydrogenation via dynamic kinetic resolution (DKR–ATH) of α,β-dehydro-α-acetamido and α-acetamido benzocyclic ketones to ent-trans-β-amido alcohols is disclosed employing a new ansa-Ru(II) complex of an enantiomerically pure syn-N,N-ligand, i.e. ent-syn-ULTAM-(CH(2))(3)Ph. DFT calculations of the transition state structures revealed an atypical two-pronged substrate attractive stabilization engaging the commonly encountered CH/π electrostatic interaction and a new additional O=S=O···HNAc H-bond hence favoring the trans-configured products.
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spelling pubmed-67508762019-09-19 trans-Diastereoselective Ru(II)-Catalyzed Asymmetric Transfer Hydrogenation of α-Acetamido Benzocyclic Ketones via Dynamic Kinetic Resolution Cotman, Andrej Emanuel Lozinšek, Matic Wang, Baifan Stephan, Michel Mohar, Barbara Org Lett [Image: see text] A highly efficient enantio- and diastereoselective catalyzed asymmetric transfer hydrogenation via dynamic kinetic resolution (DKR–ATH) of α,β-dehydro-α-acetamido and α-acetamido benzocyclic ketones to ent-trans-β-amido alcohols is disclosed employing a new ansa-Ru(II) complex of an enantiomerically pure syn-N,N-ligand, i.e. ent-syn-ULTAM-(CH(2))(3)Ph. DFT calculations of the transition state structures revealed an atypical two-pronged substrate attractive stabilization engaging the commonly encountered CH/π electrostatic interaction and a new additional O=S=O···HNAc H-bond hence favoring the trans-configured products. American Chemical Society 2019-05-06 2019-05-17 /pmc/articles/PMC6750876/ /pubmed/31058516 http://dx.doi.org/10.1021/acs.orglett.9b01069 Text en Copyright © 2019 American Chemical Society This is an open access article published under a Creative Commons Attribution (CC-BY) License (http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html) , which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.
spellingShingle Cotman, Andrej Emanuel
Lozinšek, Matic
Wang, Baifan
Stephan, Michel
Mohar, Barbara
trans-Diastereoselective Ru(II)-Catalyzed Asymmetric Transfer Hydrogenation of α-Acetamido Benzocyclic Ketones via Dynamic Kinetic Resolution
title trans-Diastereoselective Ru(II)-Catalyzed Asymmetric Transfer Hydrogenation of α-Acetamido Benzocyclic Ketones via Dynamic Kinetic Resolution
title_full trans-Diastereoselective Ru(II)-Catalyzed Asymmetric Transfer Hydrogenation of α-Acetamido Benzocyclic Ketones via Dynamic Kinetic Resolution
title_fullStr trans-Diastereoselective Ru(II)-Catalyzed Asymmetric Transfer Hydrogenation of α-Acetamido Benzocyclic Ketones via Dynamic Kinetic Resolution
title_full_unstemmed trans-Diastereoselective Ru(II)-Catalyzed Asymmetric Transfer Hydrogenation of α-Acetamido Benzocyclic Ketones via Dynamic Kinetic Resolution
title_short trans-Diastereoselective Ru(II)-Catalyzed Asymmetric Transfer Hydrogenation of α-Acetamido Benzocyclic Ketones via Dynamic Kinetic Resolution
title_sort trans-diastereoselective ru(ii)-catalyzed asymmetric transfer hydrogenation of α-acetamido benzocyclic ketones via dynamic kinetic resolution
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6750876/
https://www.ncbi.nlm.nih.gov/pubmed/31058516
http://dx.doi.org/10.1021/acs.orglett.9b01069
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