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Vinylcyclopropanes cyclopentene ring

The thermal expansion of a vinylcyclopropane to a cyclopentene ring is a special case of a [l,3]-sigmatropic migration of carbon, although it can also be considered an internal [ 2 + 2]-cycloaddition reaction (see 15-63). It is known as a vinylcyclopropane rearrangementThe reaction has been carried out on many vinylcyclopropanes bearing various substituents in the ring or... [Pg.1656]

Cyclopentene ring from vinylcyclopropanes Stereospecific cyclopentene annelation... [Pg.195]

The synthesis of useful organic motifs via molecular rearrangement of strained molecules continues to be an area of profound interest to synthetic chemists. The strain energy of a variety of three-membered carbocycles has been utilized to develop new synthetic transformations. One of the important reactions that has been ejq)lored within this class of molecules is the vinylcyclopropane (VCP)-cyclopentene (CP) rearrangement, which involves the formation of a cyclopentene ring from the ring expansion of the VCP via C—C bond cleavage fScheme 11.11. [Pg.396]

Thermal Reactions.—Vinylcyclopropanes and Related Compounds. The vinyl-cyclopropane rearrangement " provides a convenient method for cyclopentene ring formation even in highly constrained ring-fused systems. A trans-... [Pg.58]

Adducts derived from cyclopropyl-TMM reactions are versatile synthetic intermediates. Alkylidenecyclopropanes have been proven useful in further Pd-cata-lyzed transformations [4], On the other hand, vinylcyclopropanes can undergo smooth thermal ring-expansion to cyclopentenes. Thus, a total synthesis of 11-hy-droxyjasionone (27) was achieved with the cyclopropyl-TMM cycloaddition as the crucial step, and the thermal rearrangement of the initial adduct (28) as an entry to the bicyclo[6.3.0]undecyl compound (29), a key intermediate in the synthetic sequence (Scheme 2.9) [19]. [Pg.64]

The direction of ring opening by homolytic cleavage of a cyclopropane bond is controlled by the stability of the diradical species formed. Upon heating of the mono-deuterated vinylcyclopropane 3, a mixture of the two isomeric mono-deuterated cyclopentenes 4 and 5 is formed ... [Pg.282]

One other 100% atom economic rearrangement is worth mentioning briefly. When vinylcyclopropanes are heated they readily undergo ring expansion to cyclopentenes. The temperature required varies significantly, depending on the molecule for example l-phenyl-2-vinylcyclopropane may be converted to phenylcyclopentene in reasonable yield at 200 °C. [Pg.23]

The photoindueed 1,7-cycloaddition of carbon monoxide across the divinyl-cyclopropane derivative 32 yields the two cyclic dienyl ketones 34, via the ferracyclononadiene intermediate 33 [18]. (Scheme 11) cyclopentene rearrangement. The dienylcyclopropane 35 is capable of forming the complex 36, followed by ring enlargement to 37 [19]. 1,1-Dicyclopropylethylene 29 is also converted to the 1-cyclopropyl-1-cyclopentene 38. The additional functionality of vinylcyclopropanes is necessary to serve as a 7t-donor... [Pg.111]

Vinylcyclopropanes are now widely used as precursors to five-membered rings. Various methods have been designed to construct vinylcyclopropanes and bring about their rearrangement — most frequently thermolytically — to cyclopentenes. [Pg.5]

The extrapolation of the vinylcyclopropane-cyclopentene rearrangement to a vinyl-cyclobutaiie-cyclohexene synthesis begins to create new insights into the synthesis of six membered ring natural products. The eudesmane sesquiterpene (—)-P-selinene, 217 illustrates such a strategy as summarized in Scheme 14 80). A suitable cyclohexene... [Pg.80]

Several photochemically induced vinylcyclopropane to cyclopentene rearrangements of nor-carene derivatives to form bicyclo[3.2.0]heptenes can be understood as ring contractions of cyclohexenes to cyclobutanes. Upon direct irradiation of norcar-2-ene (bicyclo[4.1.0]hept-2-ene) at 214 nm (pentane solution), however, complex product mixtures were obtained containing only small amounts of bicyclo[3.2.0]hept-2-ene, while toluene sensitized photolysis in 50 millimolar solution in degassed pentane at 254 nm gave mainly the cyclobutane derivative 13 in addition to EjZ-isomeric hepla-l,3,6-trienes.72... [Pg.364]

The vinylcyclopropane radical cation, generated at 77 K by X-irradiation of (139) in a Freon-113 matrix, was shown to rearrange at 105-110 K to afford two ring-opened distonic radical cationic species.300 The rearrangement reactions of the radical cations of 1,3- and 1,4-pentadiene and cyclopentene and the formation of spin adducts with 2.4.6-tri-/-butylnitrosobenzene (BNB) are discussed. The pulse radiolysis of 1,1 -binaphthyl-2,2,-diyl hydrogenphosphate (BiNPCUH) (140) in deaerated f-butanol at... [Pg.170]

Donor-acceptor-substituted vinylcyclopropanes such as (203) have been shown to undergo thermal ring enlargement to functionalized cyclopentene derivatives (204) at... [Pg.522]


See other pages where Vinylcyclopropanes cyclopentene ring is mentioned: [Pg.1443]    [Pg.158]    [Pg.64]    [Pg.29]    [Pg.421]    [Pg.851]    [Pg.543]    [Pg.1124]    [Pg.158]    [Pg.46]    [Pg.1013]    [Pg.292]    [Pg.428]    [Pg.300]    [Pg.88]    [Pg.22]    [Pg.50]    [Pg.152]    [Pg.9]    [Pg.53]    [Pg.97]    [Pg.148]    [Pg.535]    [Pg.322]    [Pg.288]    [Pg.157]    [Pg.68]    [Pg.1128]    [Pg.263]    [Pg.5]    [Pg.49]    [Pg.1048]   
See also in sourсe #XX -- [ Pg.31 ]

See also in sourсe #XX -- [ Pg.31 ]




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Cyclopenten

Cyclopentene

Cyclopentene ring

Cyclopentenes

Cyclopentenes vinylcyclopropanes

Vinylcyclopropanation

Vinylcyclopropane

Vinylcyclopropane-Cyclopentene

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