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.

Journal Article | Published | English

No fulltext has been uploaded

Author
; ;
Abstract
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.
Publishing Year
ISSN
eISSN
PUB-ID

Cite this

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.
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.
This data publication is cited in the following publications:
This publication cites the following data publications:

60 References

Data provided by Europe PubMed Central.


Wiberg, Journal of the American Chemical Society 98(5), 1976
Planar tetrakoordinierter Kohlenstoff in einem neutralen gesättigten Kohlenwasserstoff: theoretischer Entwurf und Charakterisierung
Rasmussen, Angewandte Chemie 111(19), 1999
Inverted and Planar Carbon
Agosta, 1992
Fenestranes in Recent Synthetic Developments
Thommen, Synlett 1997(3), 1997
Benzoanellated Centropolyquinanes, 15. Benzoanellated Fenestranes with [5.5.5], [5.5.5.6], and [5.5.5.5] Frameworks: The Route from 1,3-Indandione to Fenestrindan
Kuck, Chemische Berichte 127(2), 1994
Zwei stereoisomere [4.5.5.5]Fenestrane durch intramolekulare [2 + 2]-Cycloaddition
Keese, Angewandte Chemie 104(3), 1992
Octaplan: ein gesättigter Kohlenwasserstoff mit ungewöhnlich niedriger Ionisierungsenergie und einem planar-tetrakoordinierten Kohlenstoffatom im Radikalkation
Lyons, Angewandte Chemie 106(15-16), 1994
Verbindungen mit planar tetrakoordiniertem Kohlenstoff
Röttger, Angewandte Chemie 109(8), 1997
Centrohexacyclic or “K5” Molecules: Development of a Growing Family of Topologically Nonplanar Organic Compounds
Kuck, Liebigs Annalen 1997(6), 1997
Centropentaindan, a Fenestrane Bearing Five Mutually Fused Indan Units: Syntheses, Molecular Structure, and Bridgehead Substitution
Kuck, Chemistry - A European Journal 2(1), 1996

Export

0 Marked Publications

Open Data PUB

Web of Science

View record in Web of Science®

Sources

PMID: 11531125
PubMed | Europe PMC

Search this title in

Google Scholar