Benzoannelated cis,cis,cis,trans-[5.5.5.6]fenestranes: Syntheses, base lability, and flattened molecular structure of strained epimers of the all-cis series

Bredenkötter B, Flörke U, Kuck D (2001)
CHEMISTRY-A EUROPEAN JOURNAL 7(15): 3387-3400.

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Zeitschriftenaufsatz | Veröffentlicht | Englisch
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Abstract / Bemerkung
Tribenzofenestranes possessing the strained cis,cis,cis.trans[5.5.5.6]-fenestrane skeleton have been synthesized from cis-2.6-diphenylspiro[cyclohexane-1.2 ' -indane]-1 ' .3 ' -diols by twofold cyclodehydration, in striking analogy to the strategy used previously to construct the stereoisomeric all-cis-tribenzo[5.5.5.6]fenestranes from the corresponding trans-diphenylspirodiols. In this manner, both of the parent hydrocarbons, all-cis-tribenzo[5.5.5.6]fenestrane 3 and cis.cis.cis.trans-tribenzo[5.5.5.6]fenestrane 4, have been made accessible from the spirodiketones 5 and 6, respectively. The C6-functionalized derivatives of 4-cis.cis.cis.trans-fenestranol 9 and cis.cis.cis.trans-fenestranone 12-were prepared through cis-diphenylspirotriol 8 and cis-diphenyldispiroacetaldiol 11. by using the same strategy. The cis,cis, cis.trans-[5.5.5.6]fenestrane framework readily epimerizes to the more stable all-cis isomers under basic conditions, but is stable under neutral or acidic conditions. For example, cis,cis.cis.trans-fenestranone 12 yielded all-cis fenestrane 3 under Wolff-Kishner conditions, but cis,cis,cis,trans-isomer 4 under Clemmensen conditions. Epimerization was also circumvented by radical-induced desulfurization of fenestrane dithiolane 15 with nBu(3)SnH/AIBN. producing 4 in excellent yields. A single-crystal X-ray structure analysis of 4 revealed that, in accordance with force field and semi-empirical MO calculations. the extra strain of the benzoannelated cis,cis,cis,trans-[5.5.5.6]fenestratriene framework [E-strain(4)- E-strain(3) = 46 kJ mol(-1)] is due both to the almost perfect boat conformation of the six-membered ring and to considerable bond angle widening at the central non-bridged C4b-Cl5d-C11b unit (121). H/D exchange experiments with the cis cis,cis,trans hydrocarbon 4 under basic conditions demonstrated that the strain-induced epimerization to 3 occurs through direct deprotonation of the "epimeric" benzylic bridgehead C7a-H bond, which was found to be more acidic than the two C-H bonds at the benzhydrylic bridgeheads.
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Zeitschriftentitel
CHEMISTRY-A EUROPEAN JOURNAL
Band
7
Zeitschriftennummer
15
Seite
3387-3400
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eISSN
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Bredenkötter B, Flörke U, Kuck D. Benzoannelated cis,cis,cis,trans-[5.5.5.6]fenestranes: Syntheses, base lability, and flattened molecular structure of strained epimers of the all-cis series. CHEMISTRY-A EUROPEAN JOURNAL. 2001;7(15):3387-3400.
Bredenkötter, B., Flörke, U., & Kuck, D. (2001). Benzoannelated cis,cis,cis,trans-[5.5.5.6]fenestranes: Syntheses, base lability, and flattened molecular structure of strained epimers of the all-cis series. CHEMISTRY-A EUROPEAN JOURNAL, 7(15), 3387-3400. doi:10.1002/1521-3765(20010803)7:15<3387::AID-CHEM3387>3.0.CO;2-6
Bredenkötter, B., Flörke, U., and Kuck, D. (2001). Benzoannelated cis,cis,cis,trans-[5.5.5.6]fenestranes: Syntheses, base lability, and flattened molecular structure of strained epimers of the all-cis series. CHEMISTRY-A EUROPEAN JOURNAL 7, 3387-3400.
Bredenkötter, B., Flörke, U., & Kuck, D., 2001. Benzoannelated cis,cis,cis,trans-[5.5.5.6]fenestranes: Syntheses, base lability, and flattened molecular structure of strained epimers of the all-cis series. CHEMISTRY-A EUROPEAN JOURNAL, 7(15), p 3387-3400.
B. Bredenkötter, U. Flörke, and D. Kuck, “Benzoannelated cis,cis,cis,trans-[5.5.5.6]fenestranes: Syntheses, base lability, and flattened molecular structure of strained epimers of the all-cis series”, CHEMISTRY-A EUROPEAN JOURNAL, vol. 7, 2001, pp. 3387-3400.
Bredenkötter, B., Flörke, U., Kuck, D.: Benzoannelated cis,cis,cis,trans-[5.5.5.6]fenestranes: Syntheses, base lability, and flattened molecular structure of strained epimers of the all-cis series. CHEMISTRY-A EUROPEAN JOURNAL. 7, 3387-3400 (2001).
Bredenkötter, Björn, Flörke, Ulrich, and Kuck, Dietmar. “Benzoannelated cis,cis,cis,trans-[5.5.5.6]fenestranes: Syntheses, base lability, and flattened molecular structure of strained epimers of the all-cis series”. CHEMISTRY-A EUROPEAN JOURNAL 7.15 (2001): 3387-3400.

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