1998
DOI: 10.1002/(sici)1099-1395(199805)11:5<362::aid-poc34>3.0.co;2-f
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Unusual reactivity of highly strained cyclophanes

Abstract: An essential feature of the concept of aromaticity has been the stability and lack of reactivity of aromatics relative to that of other unsaturated compounds. Contrary to this general experience, high and unusual reactivity is encountered when simple, monocyclic benzene rings are bent by short bridges into a boat-shaped conformation, as is the case in small [n] paracyclophanes (n 8) and [n]metacyclophanes (n 7). This is illustrated, mostly with examples taken from the authors' own work, for thermal and photoch… Show more

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Cited by 27 publications
(8 citation statements)
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References 35 publications
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“…Thus it would seem that differences in bond lengths exert a more pronounced effect on the degree of bend in the pyrene moiety. This being the case, the judicious incorporation of heteroatoms in the tethers of [ n ](2,7)pyrenophanes should provide a means for fine-tuning the bend of the pyrene unit, much like Bickelhaupt has done for the fine-tuning of the [5]metacyclophane system …”
Section: Resultsmentioning
confidence: 99%
“…Thus it would seem that differences in bond lengths exert a more pronounced effect on the degree of bend in the pyrene moiety. This being the case, the judicious incorporation of heteroatoms in the tethers of [ n ](2,7)pyrenophanes should provide a means for fine-tuning the bend of the pyrene unit, much like Bickelhaupt has done for the fine-tuning of the [5]metacyclophane system …”
Section: Resultsmentioning
confidence: 99%
“…by bending the aromatic ring as in small cyclophanes. 16 Recently, we reported the synthesis of the transition metal complexed 7-phosphanorbornadiene 6 by the unprecedented 1,4-addition of PhPW(CO) 5 (2a) to the highly bent [5]metacyclophane (5) (Scheme 4). 17 The extraordinary thermal stability of 6 was explained by the unfavorable thermodynamics for the retro reaction as the strain in 5 is much higher than that in 6.…”
Section: Resultsmentioning
confidence: 99%
“…Although the diyne moiety is not deformed (bond angles 177−179°) the acetylene carbons (C(12), C(13), C(24), and C(25)) are moderately distorted from linearity (165−172°). The tert -butyl-substituted benzene ring is not much distorted (α = 2.3° (for plane C(14)−C(22)−C(23)) and 0.6° (for plane C(15)−C(16)−C(21)), β = 4.6° (for bond C(13)−C(14)) and 4.9° (for bond C(22)−C(24))) . The distance between H(9) and the transannular sp carbons (C(3) and C(4)) is relatively short (2.76 and 2.74 Å, respectively).…”
mentioning
confidence: 99%