No single polymerase has been found that is able to carry out TLS past a 6-4 PP, which produces a much greater distortion in the DNA than a CPD. Lewis acid-promoted oxazaborolidine (see Section was also an efficient catalyst for asymmetric [2 + 2] cycloaddition (eqn [20]).39 The reaction of a cyclic silyl enol ether with an acrylate achieved the enantioselective construction of a chiral six–four bicyclic system. Although no particular close $\ce{H-H}$ contacts were observed, an averaged ring is considered planar: Most importantly, electron density map suggests rather increased $\mathrm{p}$-character in hybridisation (like $\mathrm{sp^5}$ in case of cyclopropane) with higher $\pi$-character of $\ce{C-C}$ bonds in comparison with the one expected for expected for alkanes: The residual electron density shows significant maxima in positions between the carbon atoms. Carrie L. Partch, Aziz Sancar, in Encyclopedia of Biological Chemistry, 2004. These maxima are displaced tangentially by $\pu{0.10(3) A}$ to the outside of the $\ce{C-C}$ bond vectors of the time- and space-averaged molecule, indicating a "banana bond" type electronic arrangement which is frequently found in highly strained small ring systems. The bond angles between carbon atoms are significantly strained and as such have lower bond energies than related linear or unstrained hydrocarbons, e.g. Compound (428) and alkyne (429) yield product (430) (75% yield) in acetonitrile at 110 °C and product (431) (58% yield) in toluene at 110 °C 〈87CB1427〉. Cyclopropane is the only cycloalkane that is planar. By clicking “Post Your Answer”, you agree to our terms of service, privacy policy and cookie policy. Such a review can of course be presented in many ways; we found it most practical to look at the structural complexity starting with the most simply substituted cyclobutanes and have organized it according to the degree of fusion to other rings. In short, cyclobutane adopts a certain, non-planar, configuration in order to reduce ring strain caused by the fact that carbons are s p 3 hybridised. However two polymerases acting in concert are able to accomplish this. Maleic anhydride reacts with enamine (432; R1 = Me, Et; R2 = H, Me) giving pyranopyridtriones (433) (9–27% yield) 〈80S698〉, and a mechanism has been proposed for this transformation. The cyclobutane ring (C5A-C5B-C6B-C6A) in the thymine dimer radical cation changes to two ethylene moieties (C5A=C6A and C5B=C6B) after the fragmentation: each of the C atoms in the cyclobutane ring changes its character from pyramidal sp3 to planar sp2. The subsequent acid-catalyzed ring opening gave an α-amino acid derivative that contained an α,β-unsaturated acyl silane moiety. TL;DR Planar structure is definitely possible, and more so in solid state as a statistically averaged geometry in space and time (in gaseous state ring is bent by $35^\circ$). From [2] and references therein: The gas-phase equilibrium conformation, as derived from electron diffraction and spectroscopic experiments, is nonplanar with a dihedral angle of about $35^\circ$ and an inversion barrier of only $\pu{6 kJ mol^-1}$. Upon binding the damaged DNA, the enzyme first thermally converts the (6-4) photoproduct to a four-membered ring intermediate closely resembling a cyclobutane dimer. The most direct synthesis is an asymmetric [2 + 2] cycloaddition. Interesting, your hybridization numbers would suggest that 1) the $\ce{C-H}$ bond in cyclobutane is somewhat more acidic than the $\ce{C-H}$ bond in cyclopropane and that 2) cyclobutane should give a positive bromine-water test as does cyclopropane.


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