11 Dihydrojervineおよび関連化合物のC/D環の立体化学

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Dihydrojervine (2) has been reported to possess α-hydrogens at both C-12 and C-13 on the basis of the chemical behavior of its degradation product 4, whose configuration has been assigned as α-H at the carbons. The present paper describes that the configuration should be revised as shown by formula 2. Compound 6b, obtained by hydrogenation of 4b, gave its deoxo derivative (9a) by the Wolff-Kishner reaction. A series of reactions summarized in Charts 2, 3 and 4 indicates that these compounds have to be formulated as 9 and 6. These revised formulae lead to revision of configuration assigned for other degradation products 5, 7 and 8. On the other hand, compounds 26 and 10, which are formed by the Birch reduction of 11-deoxojervine (28) and jervine (1), respectively, and have a double bond at C-13-C-17, have been confirmed to be cis-fused at C/D linkage by a series of reactions shown in Charts 5 and 6. ORD curves and NMR spectra of a number of these and other compounds derived from 1 were measured and parts of the results are summarized in Tables 1 and 2. In view of the spectral data of these compounds and 2, coupling constants between hydrogens at C-12 and C-13 of compounds 41 and 42 derived from 2 as well as the chemical behavior of 2 (Charts 1 and 7), it is concluded that dihydrojervine should be formulated as 2 (trans-fused C/D linkage). In addition, on the basis of these revised assignments, anomalous behavior in the hydrogenation of 1 and its various derivatives is satisfactorily explained.
天然有機化合物討論会の論文
1968-09-20

11 Dihydrojervineおよび関連化合物のC/D環の立体化学

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