Study of a Vinylidenecarbene−Cycloalkyne Equilibrium in the D 3-Trishomocubyl Ring System

Study of a Vinylidenecarbene−Cycloalkyne Equilibrium in the D 3-Trishomocubyl Ring System

The same cage-annulated vinylidenecarbene, 7a, could be generated and subsequently trapped in situ by cyclohexene via either of the following methods:  (i) low-temperature reaction of 4-(dibromomethylene)pentacyclo[6.3.0.02,6.03,10.05,9]undecane (6) with n-BuLi−THF and (ii) low-temperature reaction...

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Veröffentlicht in:Journal of the American Chemical Society 1998-07, Vol.120 (28), p.6871-6876
Hauptverfasser: Marchand, Alan P, Namboothiri, I. N. N, Ganguly, Bishwajit, Bott, Simon G
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container_issue 28
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container_title Journal of the American Chemical Society
container_volume 120
creator Marchand, Alan P
Namboothiri, I. N. N
Ganguly, Bishwajit
Bott, Simon G
description The same cage-annulated vinylidenecarbene, 7a, could be generated and subsequently trapped in situ by cyclohexene via either of the following methods:  (i) low-temperature reaction of 4-(dibromomethylene)pentacyclo[6.3.0.02,6.03,10.05,9]undecane (6) with n-BuLi−THF and (ii) low-temperature reaction of 5-bromopentacyclo[7.3.0.02,7.03,11.06,10]dodec-4-ene (12) with LDA−THF. These results, together with the corresponding results of site-specific 13C-labeling experiments performed on 6-C(4)13CBr2 and 12-13C(5), provide evidence for the thermodynamic stability of 7a vis-à-vis 7b. In addition, the results of semiempirical and ab initio MO calculations demonstrate the relative kinetic as well as thermodynamic preference for 7a vis-à-vis 7b.
doi_str_mv 10.1021/ja974313e
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