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. 2019 Jun 14;75(24):3265-3271.
doi: 10.1016/j.tet.2019.04.028. Epub 2019 Apr 25.

Thioallenoates in Catalytic Enantioselective [2+2]-Cycloadditions with Unactivated Alkenes

Michael L Conner  1 , Johannes M Wiest  1 , M Kevin Brown  1
Affiliations

Thioallenoates in Catalytic Enantioselective [2+2]-Cycloadditions with Unactivated Alkenes

Michael L Conner et al. Tetrahedron. .

Abstract

The application of thioallenoates to catalytic enantioselective [2+2]-cycloadditions with unactivated alkenes is reported.In many cases, the thioallenoates examined exhibit superior reactivity and selectivity compared to the alkoxy analogs generally used in these cycloadditions.

Keywords: Allenes; Cycloaddition; Cyclobutane; Enantioselective; Lewis-Acid.

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Figures

Scheme 1:
Scheme 1:
Catalytic Enantioselective [2+2] Cycloadditions.
Scheme 2:
Scheme 2:
Overview of work
Scheme 3:
Scheme 3:
Synthesis of Thioallenoate 9
Scheme 4:
Scheme 4:
Substrate Scope with Alkenesa a With 5 equiv alkene. See the Supporting Information for experimental details. Yields reported are the average of two experiments. Enantiomeric ratios (er) determined by HPLC analysis with a chirai column. b Previously reported in ref 3a c Previously reproted in ref 3c. d With 53 mol % 3 and 50 mol % HNTf2 e With 53 mol % 3, 50 mol % HNTf2 and 10 equiv alkene in the absence of CH2CI2. f Reaction run with oxazaborolidine 34 instead of 3 and at −17 °C.
Scheme 5:
Scheme 5:
Synthesis and use of Thioallenoate 32
See this image and copyright information in PMC

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