Strain of cyclobutane

Problem 9.9 Explain why the ring strain of cyclobutane is only slightly less than that of cyclopropane. ... 

Cyclopropane (115 kj/mol strain) and cyclobutane (110.4 kj/mol strain) have both angle strain and torsional strain. Cyclopentane is free of angle strain but has a substantial torsional strain due to its large number of eclipsing interactions. Both cyclobutane and cyclopentane pucker slightly away from planarity to relieve torsional strain. 

As mentioned previously, the Stille reaction can also be combined with an elec-trocyclization. Trauner and coworkers [99] used this approach for the synthesis of a part of SNF4435C (6/1-190) and its natural diastereomer. SNF4435C, which was isolated from the culture broth of an Okinawan strain of Streptomyces spectabilis, acts as an immunosuppressant and multidrug resistance reversal agent [100]. In order to form the annulated cyclobutane skeleton in 6/1-190, the vinyl iodide... 

The internal angles of cyclobutane are 88° => considerably angle strain. 

Cleavage of cyclobutane rings can occur easily. As indicated in the introductory section, the strain of the four-membered ring, the substituents on the ring, the nature of the reagents as well as the conditions of reaction are all responsible for the ease of cleavage of cyclobutanes 3). The substituents on the ring constitute one of the... 

Strained molecules such as cyclopropanes and cyclobutanes have emerged as important intermediates in organic synthesis. We have already demonstrated here that cyclobutane derivatives can indeed serve as starting materials for the synthesis of natural as well as unnatural products. Unlike cyclopropanes, which can be prepared asymmetrically in a number of ways 175 -182>, the asymmetric synthesis of cyclobutane derivative has received less attention, and, to our best knowledge, very few reports were recorded recently 183). Obviously, the ready availability of chiral cyclobutane derivatives would greatly enhance their usefulness in the enantioselective synthesis of natural products. The overcome of this last hurdle would allow cyclobutane derivatives to play an even more important role in synthetic organic chemistry. 

The very low value of the energy of activation for this isomerization is of considerable interest. Comparison with the decomposition of cyclobutane shows a reduction of 30 kcal mole caused by the presence of the double bond. If a similar transition state were involved in both reactions, then this difference would be a measure of the extra strain energy of the cyclobutene. This is quite unrealistically high. Thus we eliminate the possibility that the reaction path is as shown below ... 

The formation of a highly strained transient cyclobutane which undergoes cleavage has been invoked to account for the formation of three novel... 

The synthetic potential of cyclobutane cycloreversions can be demonstrated by the reactions shown below. For example, the strain inherent in hexacyclo[5.4.1.02 6.03,1°.05,9.08,11]dodecane-... 

Pinacol rearrangement driven by the release of the ring strain of a cyclobutane ring has been employed in an extremely efficient manner to form cyclopentanone derivatives. Experimentally. the Lewis acid mediated aldol condensation of benzaldehyde with l,2-bis(trimethyl-siloxy)cyclobutcne at —78 C gave the pinacol 1 in its silylated form.35,36 Subsequent treatment of this pinacol with trifluoroacetic acid at room temperature afforded 2-phenyl-cyclopentane-l,3-dione (2) in 97% yield.35,36... 

Many highly strained cage molecules undergo rearrangement when treated with metallic ions such as Ag+, Rh(I), or Pd(II).580 The bond rearrangements observed can be formally classified into two main types (1) 2 + 2 ring openings of cyclobutanes and (2) conversion... 

Several authors have pointed out that the conventional strain energy (CSE) of 1 (27.5 kcal mol1) is about of the same magnitude as that of cyclobutane (26.5 kcal mol1) and there-... 

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