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Bicyclobutane

Bicyclo[1.1.0]butane is an organic compound with the formula C<sub>4</sub>H<sub>6</sub>. It is a bicyclic molecule consisting of two cis-fused cyclopropane rings, and is a colorless and easily condensed gas. Bicyclobutane is noted for being one of the most strained compounds that is isolatable on a large scale

Manufacture and properties

Bicyclobutane is highly strained&nbsp;&mdash; its strain energy is estimated at 63.9&nbsp;kcal&nbsp;mol<sup>&minus;1</sup>. It is a nonplanar molecule, with a dihedral angle between the two cyclopropane rings of 123°.

The first reported bicyclobutane was the ethyl carboxylate derivative, C<sub>4</sub>H<sub>5</sub>CO<sub>2</sub>Et, which was prepared by dehydrohalogenation the corresponding bromocyclobutanecarboxylate ester with sodium hydride. The parent hydrocarbon was prepared from 1-bromo-3-chlorocyclobutane by conversion of the bromocyclobutanecarboxylate ester, followed by intramolecular Wurtz coupling using molten sodium. The intermediate 1-bromo-3-chlorocyclobutane can also be prepared via a modified Hunsdiecker reaction from 3-chlorocyclobutanecarboxylic acid using mercuric oxide and bromine:

Stereochemical evidence indicates that bicyclobutane undergoes thermolysis to form 1,3-butadiene with an activation energy of 41&nbsp;kcal&nbsp;mol<sup>&minus;1</sup> via a concerted pericyclic mechanism (cycloelimination, [σ2s+σ2a]).

Derivatives

Bicyclo[1.1.0]butanes are explored in medicinal chemistry as covalent reactive groups.

In the simplest case, double cyclopropanation of acetylene with a copper catalyst gives a 1:1 mixture of cyclopropenes and symmetric bicyclobutanes. Other symmetric bicyclobutanes form from functionalization of benzvalene.

A synthetic approach to more substituted bicyclobutane derivatives involves ring closure of a suitably substituted 2-bromo-1-(chloromethyl)cyclopropane with magnesium in THF, or methyllithium in diethyl ether (lithium-halogen exchange).

Substituted bicyclo[1.1.0]butanes can also be prepared from the reaction of iodo-bicyclo[1.1.1]pentanes with amines, thiols, and sulfinate salts:

Biological synthesis

Linolenic acid can be converted into its bicyclobutane derivative using a fusion protein produced by a strain of the cyanobacterium Anabaena sphaerica (strain PCC 7120). The other group reported a directed evolution approach, whereby engineered heme protein was expressed in E. coli and optimized for rate and yield of a substituted bicyclobutane derivative.

See also

References