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Trans-Diastereoselective Ru(II)-Catalyzed Asymmetric Transfer Hydrogenation of ?-Acetamido Benzocyclic Ketones via Dynamic Kinetic Resolution.

ABSTRACT: A highly efficient enantio- and diastereoselective catalyzed asymmetric transfer hydrogenation via dynamic kinetic resolution (DKR-ATH) of ?,?-dehydro-?-acetamido and ?-acetamido benzocyclic ketones to ent- trans-?-amido alcohols is disclosed employing a new ansa-Ru(II) complex of an enantiomerically pure syn- N, N-ligand, i.e. ent- syn-ULTAM-(CH2)3Ph. DFT calculations of the transition state structures revealed an atypical two-pronged substrate attractive stabilization engaging the commonly encountered CH/? electrostatic interaction and a new additional O?S?O···HNAc H-bond hence favoring the trans-configured products.

SUBMITTER: Cotman AE

PROVIDER: S-EPMC6750876 | biostudies-literature | 2019 May

REPOSITORIES: biostudies-literature

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

Cotman Andrej Emanuel AE Lozinšek Matic M Wang Baifan B Stephan Michel M Mohar Barbara B

Organic letters 20190506 10

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-(CH2)3Ph. DFT calculations of the transition state structures revealed an atypical two-pronged substrate attractive stabilization eng ...[more]

PMID: 31058516

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