Your browser doesn't support javascript.
loading
Second Generation Catalytic Enantioselective Nucleophilic Desymmetrization at Phosphorus (V): Improved Generality, Efficiency and Modularity.
Formica, Michele; Ferko, Branislav; Marsh, Thomas; Davidson, Timothy A; Yamazaki, Ken; Dixon, Darren J.
Afiliación
  • Formica M; Department of Chemistry, Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, OX1 3TA, Oxford, UK.
  • Ferko B; Department of Chemistry, Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, OX1 3TA, Oxford, UK.
  • Marsh T; Department of Chemistry, Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, OX1 3TA, Oxford, UK.
  • Davidson TA; Department of Chemistry, Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, OX1 3TA, Oxford, UK.
  • Yamazaki K; Division of Applied Chemistry, Okayama University, Tsushimanaka, Okayama, 700-8530, Japan.
  • Dixon DJ; Department of Chemistry, Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, OX1 3TA, Oxford, UK.
Angew Chem Int Ed Engl ; 63(18): e202400673, 2024 Apr 24.
Article en En | MEDLINE | ID: mdl-38381534
ABSTRACT
A broadly improved second generation catalytic two-phase strategy for the enantioselective synthesis of stereogenic at phosphorus (V) compounds is described. This protocol, consisting of a bifunctional iminophosphorane (BIMP) catalyzed nucleophilic desymmetrization of prochiral, bench stable P(V) precursors and subsequent enantiospecific substitution allows for divergent access to a wide range of C-, N-, O- and S- substituted P(V) containing compounds from a handful of enantioenriched intermediates. A new ureidopeptide BIMP catalyst/thiaziolidinone leaving group combination allowed for a far wider substrate scope and increased reaction efficiency and practicality over previously established protocols. The resulting enantioenriched intermediates could then be transformed into an even greater range of distinct classes of P(V) compounds by displacement of the remaining leaving group as well as allowing for even further diversification downstream. Density functional theory (DFT) calculations were performed to pinpoint the origin of enantioselectivity for the BIMP-catalyzed desymmetrization, to rationalize how a superior catalyst/leaving group combination leads to increased generality in our second-generation catalytic system, as well as shed light onto observed stereochemical retention and inversion pathways when performing late-stage enantiospecific SN2@P reactions with Grignard reagents.
Palabras clave

Texto completo: 1 Bases de datos: MEDLINE Idioma: En Revista: Angew Chem Int Ed Engl Año: 2024 Tipo del documento: Article País de afiliación: Reino Unido

Texto completo: 1 Bases de datos: MEDLINE Idioma: En Revista: Angew Chem Int Ed Engl Año: 2024 Tipo del documento: Article País de afiliación: Reino Unido