Asymmetric Synthesis of Pentasubstituted Cyclohexanes through Diphenylprolinol Silyl Ether Mediated Domino Michael/Michael Reaction

An efficient synthetic route to install chiral 1,3-dimethyl units through a double Michael reaction of crotonaldehyde and nitromethane catalyzed by diphenylprolinol silyl ether is developed. Either 1,3-syn- or 1,3-anti-dimethyl units are obtained selectively depending on the enantiomer of the diphenylprolinol silyl ether catalyst used. The side chain of pneumocandin B0 is synthesized enantioselectively by using the present method as a key step.

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Asymmetric Synthesis of Functionalized 9-Methyldecalins Using a Diphenylprolinol-Silyl-Ether-Mediated Domino Michael/Aldol Reaction

Organic Letters ◽

10.1021/acs.orglett.1c02196 ◽

2021 ◽

Author(s):

Yujiro Hayashi ◽

Hugo A. Salazar ◽

Seitaro Koshino

Keyword(s):

Asymmetric Synthesis ◽

Aldol Reaction ◽

Silyl Ether

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ChemInform Abstract: Base-Dependent Stereodivergent Intramolecular Aza-Michael Reaction: Asymmetric Synthesis of 1,3-Disubstituted Isoindolines.

ChemInform ◽

10.1002/chin.201403116 ◽

2014 ◽

Vol 45 (3) ◽

pp. no-no

Author(s):

Santos Fustero ◽

Lidia Herrera ◽

Ruben Lazaro ◽

Elsa Rodriguez ◽

Miguel A. Maestro ◽

...

Keyword(s):

Asymmetric Synthesis ◽

Michael Reaction

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Catalytic asymmetric formal synthesis of beraprost

Beilstein Journal of Organic Chemistry ◽

10.3762/bjoc.11.285 ◽

2015 ◽

Vol 11 ◽

pp. 2654-2660 ◽

Cited By ~ 11

Author(s):

Yusuke Kobayashi ◽

Ryuta Kuramoto ◽

Yoshiji Takemoto

Keyword(s):

Asymmetric Synthesis ◽

Michael Reaction ◽

Subsequent Reduction ◽

Formal Synthesis ◽

Michael Adduct ◽

Catalytic Asymmetric Synthesis ◽

Weinreb Amide ◽

Tricyclic Core ◽

Catalytic Asymmetric

The first catalytic asymmetric synthesis of the key intermediate for beraprost has been achieved through an enantioselective intramolecular oxa-Michael reaction of an α,β-unsaturated amide mediated by a newly developed benzothiadiazine catalyst. The Weinreb amide moiety and bromo substituent of the Michael adduct were utilized for the C–C bond formations to construct the scaffold. All four contiguous stereocenters of the tricyclic core were controlled via Rh-catalyzed stereoselective C–H insertion and the subsequent reduction from the convex face.

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