4724
what then can be the explanation of the observed uniform line broadening? We propose that the rearrangement process is that shown in Scheme I. This involves a symmetrical
temperature is 0 k 10". These studies are being extended to similar molecules. l 2
(CO),M
(12) This work was supported in part by the National Science Foundation under Grant No. 33142X. (13) On leave from the University of Zaragoza, Spain, under the auspices of the Program of Cultural Cooperation between the United States of America and Spain.
2b
Department of Chemistry, T e x a s A & M Unioersity College Station, Texas 77843 Received M a r c h 8, 1974
Scheme I
F. A. Cotton,* D. L. Hunter, P. Lahuertala 3
2a
/ 3 @
M(CO)3
A Synthesis of Cembrene. A 14-Membered Ring Diterpene
M(C0)J
.._.
\
I'
Sir : We wish to describe a total synthesis of cembrene (l), l-isopropyl-4,8,12-trimethylcyclotetradeca2,4,7,1l-tetraene, a monocyclic diterpene hydrocarbon structure of increasing importance in nature. Cembrene was the first example of a rapidly expanding group of diterpenes which contain a 14-membered ring, including neocembrene which is a scent-trail pheromone for termites in Australia (Nasutitermes xitiosus). Furthermore, the bicyclic derivatives, such as verticillol from a conifer,j eunicellin from Atlantic coral,6 and those diterpenes of the taxane type7 may also be re-
2d
2c
etc.
"piano-stool" intermediate, 3, with the metal atom lying over the center of a flat (or nearly flat) octagonally (or nearly) symmetric CsHBring. In terms of bonding this is a credible intermediate, since the metal atom could still serve as an acceptor of six 7r electrons, a pair of electrons in a low-lying totally symmetric T MO being left as essentially nonbonding. In terms of accessibility from the ground state configuration, 3 is also satisfactory, since, in the ground the metal atom already lies rather close to the central point that will arise as the ring becomes flat and only the two carbon atoms which form the "uncoordinated" double ( I ) (a) W. G . Duaben, W. E. Thiessen, and P. R. Resnick, J. Urg. Chem., 30, 1693 (1965); J . Amer. Chem. Soc., 84, 2015 (1962); ( b ) bond need move very much as the other six are already H. Kobayashi and S. Akiyoshi, Bull. Chem. Soc. Jap., 36, 823 (1963). essentially coplanar. (2) Cembrene from (a) pine trees, N. T. Mirov "The Genus Pinus." Obviously, one is immediately led to ask why this The Ronald Press, New York, N. Y., 1967; R. Teranishi and W. G. Dauben, unpublished results; S. Akiyoshi, Imp. Ind. Res. Inst. Rept., pathway applies for compounds 2 but not for 1. The Jap., 17, 1 (1931); P. M. Oloff, Jr., and N. T. Mirov, Amer. Pharm. Ass. answer, we believe, lies in the steric effect of the four J . Sci. Ed., 45, 77 (1956); N. T. Mirov, (i. S. Dep. A g r . , Tech. Bull., methyl groups upon a planar ring. The planar ring No. 1239 (1961); V. A. Pentegova and N. I
