The influence of hydrate formation on the Clemmensen reduction of pentacyclo [5.4.0.02,6.03,10.05,9]undecane-8,11-dione and pentacyclo[6.4.0.02,7.03,11.06,10]dodecane-9,12-dione
作者:Frans J.C. Martins、Agatha M. Viljoen、Marinda Coetzee、Louis Fourie、Philuphus L. Wessels
DOI:10.1016/s0040-4020(01)96209-x
日期:1991.11
Hydration of pentacyclo[5.4.0.02,6.03,10.05,9]undecane-8,11-dione led to the formation of a mixture of a geminal diol (80%) and a transannular hydrate (20%) and not to only the latter as previously accepted. Compounds with smaller intercarbonylic distances formed only transannular hydrates which promoted rearrangement reactions during Clemmensen reduction. The trans= annular hydrate of pentacyclo[6.4.0.02
Remarkably fast [2+2]cycloreversion in methoxy substituted Cookson's cage ketones assisted by the capto-dative substituent effect and by the through-bond interaction
1,7-Dimethoxy groups in Cookson's pentacyclic cage ketone derivatives ( and ) accelerate the thermal [2+2]cycloreversion, possibly by means of the unusual lengthening of C1C7 bond and the synergetic capto-dative stabilization of 1,4-diradical ( and ).