Cyclopropene strain

Padwa A., Fryxell G. E. Cyclization and Cycloaddition Reactions of Cyclopropenes Strain Org. Chem. 1991 1 117-166... 

The strain energy of cyclopropene is about 53 kcal/mol. The energy of a normal C—C bond is about 83 kcal/mol. If all the cyclopropene strain were concentrated in one C—C bond, then only ca. 30 kcal/mol extra energy would be required to break the bond. Indeed, cyclopropenes thermally open to vinylcarbenes with activation energies of 30—40 kcal/mol i9.38-40) (Table 3). The carbene-diradical resonance hybride 19 can also be formed from appropriately substituted vinyl-diazoalkanes (20) 41,42). 

Similarly, partially fluorinated and perfluorinated methylenecyclopropanes [57, 52], cyclopropenes [55, 84, 55], cyclobutenes [75, 56], and bicychc alkenes [57, 55, 59, 90] apparently denve dienophilic reactivity from relief of their ground-state strain during reaction Thus 2,2-difluoromethylenecyclopropane and perfluoromethylenecyclopropane undergo exclusive [244] cycloadditions [57, 52] (equations 72 and 73), whereas (difluoromethylene)cyclopropane undergoes only [24-2] cycloadditions [57]... 

Strained bicyclic compounds can be obtained e.g. when cyclopropenes are used as dipolarophiles. Reaction of 3,3-dimethylcyclopropene 7 with diazomethane 4 gives the heterobicyclic cycloaddition product 8 in 85% yield ... 

Benzocyclopropene is an intriguing example in which the electronic structure of benzene is greatly perturbed by the fusion of the smallest alicyclic ring, cyclopropene, to the aromatic system. Benzocyclopropene thus arouses theoretical interest and the high strain energy (approximately 68 kcal./mole)3 associated with the compound suggests unusual chemical reactivity. A review article has recently appeared.4... 

It is clear that simple cyclobutadienes, which could easily adopt a square planar shape if that would result in aromatic stabilization, do not in fact do so and are not aromatic. The high reactivity of these compounds is not caused merely by steric strain, since the strain should be no greater than that of simple cyclopropenes, which are known compounds. It is probably caused by antiaromaticity. ... 

Three-membered strained ring systems constitute an attractive class of molecules as synthetic intermediates [34-36]. Among them the rigid, unsaturated cyclopropenes are the key to selective useful transformations [37,38]... 

Methylene cyclopropene (5), the simplest triafulvene, is predicted to be of very low stability. From different MO calculations5 it has been estimated to possess only minor resonance stabilization ranging to 1 j3. Its high index of free valency4 at the exocyclic carbon atom causes an extreme tendency to polymerize, a process favored additionally by release of strain. Thus it is not surprising that only one attempt to prepare this elusive C4H4-hydrocarbon can be found in the literature. Photolysis and flash vacuum pyrolysis of cis-l-methylene-cyclopropene-2,3-dicarboxylic anhydride (58), however, did not yield methylene cyclopropene, but only vinyl acetylene as its (formal) product of isomerization in addition to small amounts of acetylene and methyl acetylene65 ... 

Carbene Is proved to be photolabile, and long-wavelength irradiation (A. > 515 nm) results in the irreversible formation of the strained cyclopropene 3s. The methyl shift to give p-xylene, which is energetically much more favorable, is not... 

Carbene lv is photolabile, and 400 nm irradiation produces a mixture of products.108 By comparison with calculated IR spectra the major product was identified as cyclopropene 3v. The formation of 3v is irreversible, and it cannot be thermally (by annealing the matrix) nor photochemically converted back to carbene lv. The lv -> 3v rearrangement is calculated (B3LYP/6-31G(d) + ZPE) to be endothermic by only 5.4 kcal/mol with an activation barrier of 18.2 kcal/mol. Due to the two Si-C bonds in the five-membered ring of 3v this cyclopropene is less strained than 3s, which is reflected by the smaller destabilization relative to carbene lv. The thermal energy available at temperatures below 40 K is much too low to overcome the calculated barrier of 12.8 kcal/mol for the rearrangement of 3v back to lv, and consequently 3v is stable under the conditions of matrix isolation. 

Addition of distannane to alkenes has been achieved only with strained cyclopropenes (Equation (60)).158 3,3-Disubstituted cyclopropenes undergo highly face-selective distannation in the presence of the palladium-isocyanide complex to afford m-adducts. 

On the contrary, if a highly strained cyclic olefm such as the cyclopropene 16 [20] or the norbornene derivative 17 [21] is employed, the titanacycle is cleaved to form the corresponding titanocene-alkylidene 18 or 19. This reaction is clearly enhanced by the concomitant release of intrinsic strain energy (Scheme 14.10). 

To direct a solvolytic ring opening, 2-methoxycyclopropyllithium (6) was developed as a chain extension conjunctive reagent. The failure of P-elimination to occur in 6 presumably derives from the high strain of cyclopropene and poor orbital overlap for elimination. The aldehyde adducts smoothly solvolyze to give p,Y unsaturated aldehydes (Eq. 22) 23) which are best initially isolated as their hemithioacetals. 

There are few reports of the hydrostannation of simple alkenes with metal catalysts in homogeneous solution, but steric strain in the ring causes cyclopropenes to be reactive even at —78 °C, with addition of Sn-H to the less sterically hindered face (Equation (25)). Distannation with Me3SnSnMe3 and silastannation with Me3SiSnBu3 could similarly be achieved with Pd(OH)2 as catalyst.107... 

One special case of cross metathesis is ring-opening cross metathesis. When strained, cyclic alkenes (but not cyclopropenes [818]) are treated with a catalytically active carbene complex in the presence of an alkene, no ROMP but only the formation of monomeric cross-metathesis product is observed [818,937], The reaction, which works best with terminal alkenes, must be interrupted when the strained cycloalkene is consumed, to avoid further equilibration. As illustrated by the examples in Table 3.22, high yields and regioselectivities can be achieved with this interesting methodology. 

The intermolecular reaction of alkynes with acylcarbene complexes normally yields cyclopropenes [587,1022,1060-1062]. Because of the high reactivity of cyclopropenes, however, in some of these reactions unexpected products can result. In particular intramolecular cyclopropanations of alkynes, which would lead to highly strained bicyclic cyclopropenes, often yield rearrangement products of the latter. In many instances these products result from a transient vinylcarbene complex, which can be formed by two different mechanisms (Figure 4.3). 

As discussed in Section 3.1.6, cyclopropenes can react with rhodium complexes [38,585,587-589,1061,1063] or other transition metal derivatives to yield vinylcarbene complexes (see Section 3.1.6). This reaction will proceed particularly smoothly with strained cyclopropenes, because these can already isomerize thermally to vinylcarbenes [1064]. Hence the formation of vinylcarbene complexes from alkynes can proceed by initial cyclopropanation, followed by reaction of the resulting cyclopropene with the complex L,M. 

The chemistry of cycloproparenes is characterized by the interplay of two contradictory effects, namely aromaticity which is generally known to stabilize compounds, and strain which destabilizes them. The fusion of a cyclopropene to a benzene ring results in geometrical distortions and strain which has consequences on the properties of the resulting cycloproparene. It perturbs the aromatic Ji-electron... 

In contrast, isomers of 115 have so far not been isolated. An early attempt to generate cyclopropa[a,e]naphthalene (118) failed. More recently, the generation of dicyclopropa[a,c]naphthalene (119) was attempted by reaction of 120 with base. When the aromatization was carried out in the presence of DPIBF (44), stereoi-someric bis-adducts of cyclopropenes were isolated. However, the adducts provide no evidence for the formation of 119 as a reactive intermediate, since they are formed by sequential elimination-cycloaddition via 121. Cyclopropene interception of 121 is faster than further elimination to 119. The failure of the reaction to produce 119 has been attributed to the high strain energy of the product, which is estimated some 2 8 kcal/mol higher than that expected for two isolated cyclopropene units. ... 

The consequences of the distortion of the aromatic benzene ring by fusion to a cyclopropene, as it occurs in cycloproparenes, has been the subject of much discussion and speculation. Much of this debate concerned the question of bond fixation in strained aromatics which has a long historical background. In 1930 Mills and Nixon observed different reactivities towards electrophilic substitution of the a and positions in tetralin (251) and indane (252). This observation was... 

The structures of several substituted cycloproparenes, i.e., l,l-dichloro-2,5-diphenylbenzocyclopropene (22), l,l-dimethoxycarbonyl-2,5-diphenylbenzo-cyclopropene (264), 2,5-diphenylbenzocyclopropene (265), and l//-cyclopropa[fc]naphthalene (42), have also been determined, and are consistent with those of the unsubstituted compounds. Even the most strained member of the family, dicyclopropanaphthalene (115), exhibits no further deformations than the parent 1. The cycloproparene structure is also preserved in alkylidenecyclo-proparenes with only minute changes. The exocyclic double-bond length of alky-lidenecycloproparenes lies in the range of 1.343 to 1.346 A. ... 

The strain of 1 has been determined experimentally from silver-ion catalyzed methanolysis to be ca. 68 kcal/mol, and that of cyclopropa[/j]naphthalene to be 65-67 kcal/mol. Combustion calorimetry gave a value of 67.8 kcal/mol. For dicyclopropa[/>,g]naphthalene (115) a lower limit of 166 kcal/mol was found. These energies are well reproduced by ab initio, and even by semiempirical calculations. Thus 3-2IG calculates a strain energy of 70 kcal/mol while 3-2IG gives 71.6. At the MP2/6-31G level the strain of 1 is 71.3 kcal/mol, while that of cyclopropene amounts to 57.4 kcal/mol. This latter value compares well with the experimental one, which is 52.6 kcal/mol. While semiempirical calculations have been found unreliable for cycloproparene structures, the calculated strain energies are usually close to reality for MINDO/3, MNDO, and force-field-SCF calculations. The strain energies of the dicyclopropabenzenes (100, 102) have been predicted to be 133 and 140 kcal/mol, respectively, and that of tricyclo-propabenzene (260) to be 217 kcal/mol (3-21G). ... 

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