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. 2008 Jun 4;130(22):6924-5.
doi: 10.1021/ja802906k. Epub 2008 May 8.

Rhodium(I)-catalyzed cycloisomerizations of bicyclobutanes

Maciej A A Walczak  1 , Peter Wipf
Affiliations

Rhodium(I)-catalyzed cycloisomerizations of bicyclobutanes

Maciej A A Walczak et al. J Am Chem Soc. .

Abstract

The selection of rhodium precatalyst and phosphine ligand determines the course of the cycloisomerization of N-allylated bicyclo[1.1.0]butylalkylamines. Cyclopropane-fused pyrrolidines and azepines are obtained with high levels of stereo- and regiocontrol. Novel azatricyclo[6.1.0.0(1,5)]nonanes are the result of a tandem cycloisomerization-ring closing metathesis sequence. Allylic ethers lead to furans and oxepanes.

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Figures

Scheme 1
Scheme 1
Furan and Oxepane from Allylic Ether
Scheme 2
Scheme 2
Proposed Mechanism of Cycloisomerization Reactions
Scheme 3
Scheme 3
Synthesis of 3-Azatricyclo[6.1.0.01,5]nonanes via Tandem Isomerization-RCMa a Reagents and conditions: (a) [Rh(=)2Cl]2, Ph3P, PhMe, 110 °C then metathesis catalyst, 60 °C; (b) i. Na/naphthalene, THF, -78 °C; ii. PhCOCl, DMAP, Et3N, CH2Cl2,0 °C, 53%.
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