The Carbenoid Dihalotriangulane Rearrangement: A Mechanistic Mystery

Abstract

This account focuses on the unprecedented carbenoid ­rearrangement of dihalotriangulanes promoted by treatment with methyllithium. This rearrangement reaction proceeds via a wide variety of intermediates, including carbenoids, carbenes, cations, and organolithium species as well as different halides. Mutual interactions between these intermediates lead to a variety of unusual rearrangement products. The scope and limitations of the unusual dihalotriangulane rearrangement are outlined and some surprising mechanistic features of the reaction are discussed.

1 Introduction

2 First Mechanistic Step: Formation of Carbenoids

3 Ensuing Mechanistic Steps: Transformations of Carbenoids

3.1 Conversions of Carbenoids into Carbenes

3.2 Skeletal (Carbocation-like) Rearrangements of Carbenoids

3.3 Further Transformations of Rearranged Carbenoids

4 Involvement of Intermediate Cations in Other Electrophilic Transformations

5 Final Mechanistic Steps

5.1 Halogenophilic Transformations of Intermediate Organolithiums

5.2 Formation of ‘Dimeric’ Structures

5.3 Transformations of Fluoro-Containing Substrates into ­Methylated Products

5.4 Pathway Involving the Substitution of Lithium by Hydrogen

6 Conclusion

Key words

gem-dihalo-substituted triangulanes - carbenoids - rearrangements - carbocations - halo-substituted cyclobutenes

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11

Only one example of the unusual reactivity of gem-bromofluoropolyspirocyclopropanes is known. This involves the treatment of highly spirocyclopropanated fluorobromo[15]triangulane with butyllithium at -10 to
-5 ˚C which led to a remarkable skeletal rearrangement accompanied by two consecutive cyclopropylcarbene to cyclobutene ring enlargements and the incorporation of two n-butyl groups, resulting in a bicyclo[2.2.0]hexane derivative as the main product; this is described on p 4970 of the following: See ref. 2d.

12

This is remarkable because many publications exist concerning reactions of dibromides of type 1 with alkyllithium where the rearrangement products are not formed.

22

For clarity, we use here the pure carbocationic stepwise presentation, thus ignoring the problem of the concerted nature of mechanistic steps.

25

For simplicity, we use here only one resonance structure, 29; obviously this process may be also equivalently treated as electrophilic substitution in the aromatic ring.