Carbenoid rearrangement of gem-dihalogenospiropentanes

Averina, Elena B.; Karimov, Rashad R.; Sedenkova, Kseniya N.; Grishin, Yuri K.; Kuznetzova, Tamara S.; Зефиров, Н. С.

doi:10.1016/j.tet.2006.06.086

Cited by 17 publications

(11 citation statements)

References 31 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In our recent work 4 we have systematically studied the reaction of a number of terminal gem dibromospiropentanes with methyllithium forming dimer rearrangement products of type C (Scheme 1) in good yields. We have also investigated the reaction of several dibromospiranes containing tetrasubstituted dibromocyclopropane moieties with methyllithium, and either monomer rearrangement products B or C-H insertion products were obtained.…”

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

Reaction of polyspirocyclic internal gem-dibromocyclopropanes with methyllitium. Unusual carbenoid rearrangement

Averina¹,

Sedenkova²,

Grishin³

et al. 2008

Arkivoc

Self Cite

View full text Add to dashboard Cite

A skeletal rearrangement of a series of polyspiro internal gem dibromocyclopropanes in the presence of methyllithium reagents was studied. The rearranged products of two types were obtained: substituted bromocyclobutenes (type B) and C-H insertion products (type K) resulting from the reaction of the carbenoid intermediate H with the ether solvent. The mechanism of the carbenoid rearrangement is discussed.

show abstract

Section: Methodsmentioning

confidence: 99%

“…We thank the Division of Chemistry and Materials Science RAS (Program № 1) and the President`s grant "Support of Leading Scientific School" N 2552.2006 for financial support of this work.…”

Section: Acknowledgementsmentioning

confidence: 99%

Reaction of polyspirocyclic internal gem-dibromocyclopropanes with methyllitium. Unusual carbenoid rearrangement

Averina¹,

Sedenkova²,

Grishin³

et al. 2008

Arkivoc

Self Cite

View full text Add to dashboard Cite

show abstract

“…In contrast with its reaction with NHC, CO addition to acyclic and cyclic alkylaminocarbenes (70) forms aminoketenes (71). 57 The structure of the ketene has been fully studied (experimentally and theoretically).…”

Section: Addition and Fragmentationmentioning

confidence: 99%

“…71 The carbenoids rearrange to cyclobutenes (92), which typically undergo a second lithium-halogen exchange before dimerizing in 44-75% yield. …”

Section: Rearrangementmentioning

confidence: 99%

Carbenes and Nitrenes

Christlieb¹,

Gras²

2010

Organic Reaction Mechanisms · 2006

View full text Add to dashboard Cite

“…141 The synthesis of stable azomethine ylides by the rearrangement of 1,3-dipolar cycloadducts of 3,4-dihydroisoquinoline-2-oxides with DMAD has been described. 141 The synthesis of stable azomethine ylides by the rearrangement of 1,3-dipolar cycloadducts of 3,4-dihydroisoquinoline-2-oxides with DMAD has been described.…”

Section: Rearrangements Involving Ring Openingmentioning

confidence: 99%

Molecular Rearrangements: Part 2. Other Reactions

Brandi

Gensini

2010

Organic Reaction Mechanisms · 2006

View full text Add to dashboard Cite

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

show abstract

Carbenoid rearrangement of gem-dihalogenospiropentanes

Cited by 17 publications

References 31 publications

Reaction of polyspirocyclic internal gem-dibromocyclopropanes with methyllitium. Unusual carbenoid rearrangement

Reaction of polyspirocyclic internal gem-dibromocyclopropanes with methyllitium. Unusual carbenoid rearrangement

Carbenes and Nitrenes

Molecular Rearrangements: Part 2. Other Reactions

Contact Info

Product

Resources

About