Carbenes molecular rearrangements

In this review an attempt is made to discuss all the important interactions of highly reactive divalent carbon derivatives (carbenes, methylenes) and heterocyclic compounds and the accompanying molecular rearrangements. The most widely studied reactions have been those of dihalocarbenes, particularly dichlorocarbene, and the a-ketocarbenes obtained by photolytic or copper-catalyzed decomposition of diazo compounds such as diazoacetic ester or diazoacetone. The reactions of diazomethane with heterocyclic compounds have already been reviewed in this series. ... 

Flash vacuum thermolysis of 6-chloro-3-diazoindazole (2b) resulted, upon loss of nitrogen, in the formation of carbene 102, which could intra-molecularly rearrange to the nitrene 103, or to the azabenzocyclopropene 104, or to azacycloheptatrienylidene 105 (Scheme 29). The only isolable product was 106, formed by dimerization of the nitrene 103 (78CB2258). 

We welcome one new author to the series Prof K. C. Westaway has reviewed Nucleophilic Aliphatic Substitution in place of Prof I. Lee, whose cameo contribution to ORM 2004 is gratefully acknowledged. The contribution of Prof K. Banert and Dr H. Hahn to that volume is also particularly appreciated since it enabled the now returning author of Molecular Rearrangements, Pt 1 to enjoy a productive maternity leave. Thanks are also due to outgoing author Prof D. M. Hodgson who, following his expert contributions over several years, felt able to leave the Carbenes and Nitrenes chapter in the capable hands of his co-authors. 

Diazirine, fluoromethoxy-nitrogen extrusion, 7, 224 Diazirine, methylvinyl-rearrangement, 7, 221 Diazirines addition reactions to Grignard compounds, 7, 2 0 as carbene precursors, 7, 236 IR spectra, 7, 203 microwave spectrum, 7, 199 molecular spectra, 7, 202-204 nitrogen extrusion, 7, 223 NMR, 7, 202 photoconversion to diazoalkanes, 7, 234 photoisomerization, 7, 221 photolysis, 7, 225-227 quantum chemical investigations, 7, 197 reactions... 

The facile thermal decomposition of the dimethyl and diethyl derivatives of (II) to nitrogen and carbene intermediates is emphasized by the readily discernible correlations between the reactant and product orbitals. On the other hand, the greater delocalization of the molecular orbitals of (I) may be a factor in its preference to rearrange, without decomposition, to methyl acetylene and allene. 

Hydride and 1,2-alkyl shifts represent the most common rearrangement reactions of carbenes and carbenoids. They may be of minor importance compared to inter-molecular or other intramolecular processes, but may also become the preferred reaction modes. Some recent examples for the latter situation are collected in Table 23 (Entries 1-10, 15 1,2-hydride shifts Entries 11-15 1,2-alkyl shifts). Particularly noteworthy is the synthesis of thiepins and oxepins (Entry 11) utilizing such rearrangements, as well as the transformations a-diazo-p-hydroxyester - P-ketoester (Entries 6, 7) and a-diazo-p-hydroxyketone -> P-diketone (Entry 8) which all occur under very mild conditions and generally in high yield. 

Garcia-Garibay M (2003) Engineering carbene rearrangements in crystals from molecular information to solid-state reactivity. Acc Chem Res 36 491-498... 

Although some carbenes are reported not to add to cyclopropenes207, there are several examples of inter- and intra-molecular addition leading initially to the formation of bicyclobutanes. l,2-Diphenylcyclopropene-3-carboxylates are converted to a mixture of three stereoisomeric bicyclo[1.1.0]butanes by reaction with ethoxy-carbonylcarbene generated from the thermolysis of ethyl diazoacetate an additional product is the diene (278) which is apparently formed by rearrangement of an intermediate zwitter ion208). It should be noted, however, that cyclopropenes readily undergo addition to diazo-compounds, and that subsequent transformations may then lead to bicyclobutanes (see Section 8), and that a free carbene may therefore not be involved in the above process. 

The thermal decompositions of diazirines appear to be homogeneous, uni-molecular processes " . Cyclic diazirines decompose with a slightly smaller activation energy (Table 14) due to ring strain. Product distributions presumably result from intramolecular rearrangement of carbene intermediates, and the fact that the product ratios differ from those obtained on photolysis supports the hypothesis that the carbenes generated photolytically contain considerable excess vibrational energy. 

---