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. 2017 Jan 24;56(5):1390-1395.
doi: 10.1002/anie.201608752. Epub 2016 Dec 27.

Catalytic Enantioselective and Diastereoselective Allylic Alkylation with Fluoroenolates: Efficient Access to C3-Fluorinated and All-Carbon Quaternary Oxindoles

Kaluvu Balaraman  1 , Christian Wolf  1
Affiliations

Catalytic Enantioselective and Diastereoselective Allylic Alkylation with Fluoroenolates: Efficient Access to C3-Fluorinated and All-Carbon Quaternary Oxindoles

Kaluvu Balaraman et al. Angew Chem Int Ed Engl. .

Abstract

Synthetically versatile 3,3-disubstituted fluorooxindoles exhibiting vicinal chirality centers were obtained in high yields and with excellent enantio-, diastereo-, and regioselectivity through catalytic asymmetric fluoroenolate alkylation with allylic acetates. The reaction proceeds under mild conditions and can be scaled up without compromising the asymmetric induction. The unique synthetic usefulness of the products is highlighted by the incorporation of additional functionalities and the formation of 3-fluorinated oxindoles exhibiting an array of four adjacent centers of chirality. A new C-F bond functionalization path that provides unprecedented possibilities for the stereoselective generation of a chiral quaternary carbon center in the alkaloid scaffold is introduced.

Keywords: alkaloids; homogeneous catalysis; organofluorines; quaternary chiral centers; synthetic methods.

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Figures

Figure 1
Figure 1
Top: Crystal structures of the minor (left) and the major (right) diastereomer of 3dc. Bottom: Proposed formation of the only observed two stereoisomers.
Scheme 1
Scheme 1
Asymmetric synthesis with fluorooxindoles.
Scheme 2
Scheme 2
Reaction scope of the asymmetric catalytic allylation of fluorooxindoles.
Scheme 3
Scheme 3
Regioselective asymmetric allylation with acetates 2j-m.
Scheme 4
Scheme 4
Selective transformations of 3-fluorooxindoles. The absolute and relative stereochemistry of 3da was assigned in accordance with the crystallographic data obtained with 3dc.
See this image and copyright information in PMC

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