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. 2012 Aug 13;51(33):8264-7.
doi: 10.1002/anie.201203092. Epub 2012 Jul 23.

Catalytic asymmetric Claisen rearrangement of enolphosphonates: construction of vicinal tertiary and all-carbon quaternary centers

Jiajing Tan  1 , Cheol-Hong Cheon, Hisashi Yamamoto
Affiliations

Catalytic asymmetric Claisen rearrangement of enolphosphonates: construction of vicinal tertiary and all-carbon quaternary centers

Jiajing Tan et al. Angew Chem Int Ed Engl. .

Abstract

A Cu-catalyzed enantioselective Claisen rearrangement of easily-accessible enolphosphonates using commercially available (R, R)-PhBOX as the chiral ligand was developed. A wide range of rearrangement products with contiguous tertiary and all carbon quaternary centers were obtained in excellent yields and stereoselectivities. The α-ketophosphonate products could be easily transformed into other functional groups in high efficiency.

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Figures

Figure 1
Figure 1
Claisen rearrangement of enolphosphonates
Figure 2
Figure 2
Proposed transition state
Scheme 1
Scheme 1
Synthetic applications of rearrangement product 1 DBU=1,8-Diazabicyclo[5.4.0]undec-7-ene, DIBAL-H= Diisobutylaluminium hydride, LAH=Lithium aluminium hydride
See this image and copyright information in PMC

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