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. 2019 Jul 5;21(13):5064-5067.
doi: 10.1021/acs.orglett.9b01660. Epub 2019 Jun 20.

Re2O7-Catalyzed Approach to Spirocyclic Ether Formation from Acyclic Precursors: Observation of Remote Stereoinduction

Cephas Afeke  1 , Youwei Xie  1 , Paul E Floreancig  1
Affiliations

Re2O7-Catalyzed Approach to Spirocyclic Ether Formation from Acyclic Precursors: Observation of Remote Stereoinduction

Cephas Afeke et al. Org Lett. .

Abstract

Ketones that are flanked by an allylic alcohol and an alkene isomerize to spirocyclic ethers in the presence of Re2O7 through allylic alcohol transposition, oxocarbenium ion formation, and Prins cyclization. These processes provide significant increases in molecular complexity, with multiple stereocenters being set relative to a stereocenter in the substrate. Stereoselectivity arises from the initial reversible steps being more rapid than the final step, thereby allowing for thermodynamically controlled stereochemical equilibration prior to product formation.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1.
Figure 1.
Diastereocontrol as a function of conversion. The blue line represents product yield as determined by an internal standard and is quantitated by the left y-axis. The orange line represents the ratio of 6/7 and is quantitated by the right y-axis.
Scheme 1.
Scheme 1.
Re2O7-Mediated Spiroacetal Formation
Scheme 2.
Scheme 2.
Spirocyclic Ether Formation
Scheme 3.
Scheme 3.
Relative Stereocontrol from a Chiral Substrate
Scheme 4.
Scheme 4.
Effect of Incorporating a Substituent into the Cyclohexane Subunit
Scheme 5.
Scheme 5.
Variations on the Nucleophile
See this image and copyright information in PMC

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