Synthetically Useful Wagner–Meerwein Rearrangement of α‐Quaternary β‐Bromovinyl Methyl Ethers

Wang, Aixia; Tu, Yong‐Qiang; Song, Zhenlei; Yuan, Dao-Yi; Hu, Xiangdong; Wang, Shao‐Hua; Gao, Shuanhu

doi:10.1002/ejoc.200600195

Cited by 6 publications

References 64 publications

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Wagner‐Meerwein Rearrangement

2010

Comprehensive Organic Name Reactions and Reagents

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The class of 1,2‐rearrangement of carbocation intermediates, from which the migratory group rearranges from an adjacent carbon atom to the carbocation center to form a more stable carbocation or to alleviate the ring strain, is generally known as the Wagner–Meerwein rearrangement. The Wagner–Meerwein rearrangement is generally observed in fused cyclic compounds, such as bicyclic terpene systems. In general, this rearrangement can be initiated under different conditions, which promote the generation of carbocation intermediates. However, due to the carbocationic nature of the rearrangement, this rearrangement sometimes leads to a complicated mixture of products. The modifications for this reaction include the photolysis, thermolysis of azo ‐compounds, and radical initiation of epoxide by Cp 2 TiCl and azo ‐compound by triphenyl pyrylium tetrafluoroborate. This reaction has been broadly applied in organic synthesis.

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Wagner‐Meerwein Rearrangement

2010

Comprehensive Organic Name Reactions and Reagents

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Molecular Rearrangements: Part 2. Other Reactions

Brandi

Gensini

2010

Organic Reaction Mechanisms · 2006

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The formation of α-phenyl-β-halovinyl cation, β-phenyl-α-halovinyl cation, and also the halogen-bridged and the spirocyclic phenyl-bridged cations, as intermediates of protonation of phenylethynyl halides, or of halogen addition to phenylethynes, has been evaluated by DFT at the B3LYP/6-31+G(d) level and, for comparison in representative cases, by B3LYP/6-311++G(d,p). 1 Structural and mechanistic studies of the lithium diisopropylamide (LDA)-mediated anionic Fries rearrangements of aryl carbamates have been described. 2 Substituents at the meta position of the arene (H, OMe, F) and the dialkylamino moiety of the carbamate (Me 2 N, Et 2 N, and i-Pr 2 N) markedly influence the relative rates of ortholithiation and subsequent Fries rearrangement. The mechanism of the Fries rearrangement of aryl formates promoted by boron trichloride has been studied by means of 1 H, 2 H, and 11 B NMR spectroscopy and DFT calculations. 3 After the formation of a 1:1 substrate -Lewis acid adduct, the rearrangement proceeds in two steps, beginning with the cleavage of the ester bond and the release of formyl chloride in situ, which, in turn, acts as a formylating agent, introducing 451

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