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Transition‐Metal‐Free Reduction of α ‐Keto Thioesters with Hydrosilanes at Room Temperature: Divergent Synthesis through Reagent‐Controlled Chemoselectivities
Author(s) -
Maity Rajib,
Das Bhanuranjan,
Das Indrajit
Publication year - 2019
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201900222
Subject(s) - chemistry , chemoselectivity , deoxygenation , reagent , moiety , silylation , conjugated system , thioester , organic chemistry , amine gas treating , enone , catalysis , combinatorial chemistry , medicinal chemistry , polymer , enzyme
The combination of hydrosilanes with a Brønsted or Lewis acid as a promoter can be used for the reagent‐controlled chemoselective reduction at room temperature of conjugated C=C bond, enone moiety, or the carbonyl of (β,γ‐unsaturated) α‐keto thioesters, providing facile access to β,γ‐saturated α‐keto thioesters, α‐hydroxy thioesters, or silyl ethers. The reaction pathway and the chemoselectivity can be fine‐tuned through the judicious choice of the hydrosilane or the reaction conditions. The reactions tolerate a wide range of functional groups including labile thioesters and the products are generally obtained in moderate to excellent yields. Unsymmetrical thioethers can also be synthesized using PMHS and catalytic B(C 6 F 5 ) 3 via reductive deoxygenation of both the carbonyl groups. The applicability has been highlighted by the amine‐mediated and coupling reagent‐free syntheses of saturated α‐keto amides from β,γ‐unsaturated α‐hydroxy thioesters and β,γ‐saturated α ‐keto thioesters.