Tetrahedron Letters No. 27, PP 2367- 2370, 1978.
© Pergamon Press Ltd. Printed in Great Britain.
0040-4039/78/0701-2367#02.00/0
THE STRUCTURE AND ABSOLUTE CONFIGURATION OF CHONDROCOLACTONE,
A HALOGENATED MONOTERPENE FROM THE RED ALGA CHONDROCOCCUS HORNEMANNI,
AND A REVISED STRUCTURE FOR CHONDROCOLE A
Frank X. Woolard and Richard E. Moore
Department of Chemistry, University of Hawaii, Honolulu, Hawaii 96822
*i
Donna Van Engen and Jon Clardy
Ames Laboratory-USDOE and Department of Chemistry,
Iowa State University, Ames, Iowa 50011
(Received in USA 28 March 1978; received in lie for publication 4 M~y 1978)
In an investigation of volatile compounds from Hawaiian marine algae$ we found that a cyclic
halogenated monoterpene, chondrocole A, is a major constituent in the essential oil of a
Chondrococcus hornemanni found in the vicinity of the Halona Blowhole, Oahu. From spectral
evidence, mainly PMR and mass spectral data, we assigned structure I to chondrocole A.
m
Further
study, however, in particular an X-ray crystallographic analysis of a closely-related metabollte,
chondrocolactone (2), has now shown that this structure is incorrect and that chondrocole A has
structure 3.
,j 3
R ~~~, 4",R
,d
B I
1 RI=CI, R2-Br 2
3 RI-- Br, R2=CI
Chondrocolactone (2) was isolated from the CH2CI 2 extract of the alga, using conventional
silica gel chromatography (elution with i:i CH2Cl2-hexane), as colorless needles, mp i07-i08 °
24
(recrystallization from CH2Cl2-hexane) ; [~]D -48 @ (CH2C12, c 0.62). The PMR spectrum of 2
(Table i) was similar to that of 3 except that the signal for the C-2 protons was missing. The
presence of an oxo group on C-2 (~,8-unsaturated y-lactone functionality) was indicated by the
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