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. 2015 Oct 28;137(42):13715-21.
doi: 10.1021/jacs.5b09799. Epub 2015 Oct 16.

(4+1) vs (4+2): Catalytic Intramolecular Coupling between Cyclobutanones and Trisubstituted Allenes via C-C Activation

Xuan Zhou  1 , Guangbin Dong  1
Affiliations

(4+1) vs (4+2): Catalytic Intramolecular Coupling between Cyclobutanones and Trisubstituted Allenes via C-C Activation

Xuan Zhou et al. J Am Chem Soc. .

Abstract

Herein we describe a rhodium-catalyzed (4+1) cyclization between cyclobutanones and allenes, which provides a distinct [4.2.1]-bicyclic skeleton containing two quaternary carbon centers. The reaction involves C-C activation of cyclobutanones and employs allenes as a one-carbon unit. A variety of functional groups can be tolerated, and a diverse range of polycyclic scaffolds can be accessed. Excellent enantioselectivity can be obtained, which is enabled by a TADDOL-derived phosphoramidite ligand. The bridged bicyclic products can be further functionalized or derivatized though simple transformations.

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Figures

Figure 1
Figure 1
Crystal structure of compound (±)-2a at 50% probability level. Hydrogen atoms are omitted for clarity.
Scheme 1
Scheme 1
Rhodium-catalyzed (4+1) cycloaddition initiated by C–C activation
Scheme 2
Scheme 2
Proposed Catalytic Cycle
Scheme 3
Scheme 3
Synthetic Applications
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