Diastereoselective Construction of New 5a-Substituted Carbaallose by exo-β-Selective Conjugate Addition to endo-exo Cross-Conjugated Cyclohexadienone as Key Reaction

Abstract

Practical synthesis of a new chiral endo-exo cross-conjugated cyclohexadienone was achieved, and its synthetic utility was illustrated by highly exo-β-selective conjugate addition with various nucleophiles. Further diastereoselective transformation of the adduct to an unprecedented 5a-substituted carbaallose is also described.

Key words

rearrangement of endoperoxide - cross-conjugated dienone - regioselective conjugate addition - stereoselective synthesis - carbasugar

References and Notes

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8

We have deposited the crystallographic data for 3 with the Cambridge Crystallographic Data Center as supplementary publication number CCDC 779019.

12

This byproduct could be the diastereomer of 6e. However, no confirmation has been yet obtained as these two products are not separated by TLC and their ^¹H NMR signals (600 MHz) are extensively overlapping.

14

We have deposited the crystallographic data for 10 with the Cambridge Crystallographic Data Center as supplementary publication number CCDC 779020.

15

In a preliminary experiment, the enantioenriched dienone 5 (90% ee) was obtained by asymmetric Kornblum DeLaMare rearrangement of 3 under Toste’s conditions.^¹6 For details, see the Supporting Information.