J. Am. Chem. SOC.

1980, 102, 6351-6353 6351

identical but the refractive indices, although not identical, are pose extremely easily at elevated probe and ion-source tempera-
reasonably close, considering the air sensitivity of the compound tures. As a consequence, great care was necessary in order to
and the sensitivity of such indices to i m p ~ r i t i e s . ’ ~ obtain meaningful spectra exhibiting parent mass peaks.”
Examination of the ‘H and I3C N M R data reveals only small Despite their air sensitivity and thermal instability above -80
differences between our data and that reported for “la”. These OC, the q2-vinylsilane complexes 2 are remarkably stable.
differences, as indicated in Table I, are uniform and represent (Ethylene)tetracarbonyliron, by comparison, is quite unstable and
a shift of the spectrum as a whole, a fact which strongly suggests is reported to decompose slowly above -40 oC.20 Although the
either concentration, solvent (I3C NMR), or instrumental dif- inductive effect of the silicon, which raises the energies of the A
ferences, rather than gross structural differences, e g , between and A* orbitals,” would be destabilizing, the resonance effect,
l a and 2a. involving p d A bonding and the lowering of the A* orbital,
The infrared spectra of 2a and “la” (Table 11) are virtually presumably would be stabilizing by virtue of enhanced back-do-
identical, differing in only one respect. An additional metal nation by the metal.
carbonyl band at 2080 cm-’ with weak intensity is observed by Attempts to prepare l a from 2a thermally as well as photo-
us, but is not reported by the Sakurai group for their compound. chemically have failed. In view of the evidence for the failure
Whether such a band was in fact observed but simply not reported to prepare the $-silapropenyl complex la, the validity of the
owing to its weak intensity is not clear. structure l b immediately becomes suspect. As a consequence,
The observation of an infrared absorption of medium to weak it would appear that the stabilization of a doubly bonded silicon
intensity at -1315 cm-’ in the spectra of all of the (vinyl- species by a transition metal remains to be conclusively demon-
si1ane)tetracarbonyliron complexes prepared to date is interesting strated.
in view of the suggestionZathat this absorption band, observed in
the spectrum of “la”, might be assigned to the stretching fre- Acknowledgment. Partial support by the National Science
quency of a coordinated Si=C bond. Clearly, with the present Foundation (Grant NSF-CHE-78-01764) in the purchase of the
results, such an assignment is not ~ a r r a n t e d . ’ ~The agreement Digilab FTS-20C IR spectrometer is gratefully acknowledged.
between our UV data and that reported for “la” is good,16 al- The technical assistance of Dr. J. Paul Devlin and Norman
though we fail to detect the reported shoulder at 221 nm.16‘ Perreira is also acknowledged with our thanks.
The key to the assignment of the correct structure to the
complex obtained from 3a and Fe2(C0)9 resides in the mass (20) Murdoch, H . D.; Weiss, E. Helu. Chim. Acta 1963, 46, 1588.
spectral (MS) data. As mentioned earlier, our MS data with a
parent peak at m/e 326 clearly indicate a tetracarbonyl rather P. Radnia, J. S. McKennis*
than a tricarbonyliron complex, Le., structure 2a rather than la. Department of Chemistry. Oklahoma State University
Additionally, the high relative intensity of a peak at m/e 158, Stillwater, Oklahoma 74074
corresponding to the free ligand 3a, is consistent with the pres- Received March 21. 1980
ervation of the structural integrity of 3a upon c~mplexation.”~
Although Sakurai and co-workers observed the same fragmen-
tation they failed to detect the parent mass peak and
assumed that the P-28(CO) peak was the parent peak and in-
dicative of a parent Fe(C0)3 species. Presumably, on the basis
of this assumption, in part, and the belief that the cleavage of,
or oxidative insertion in, a relatively weak Si-Si bond by a Total Synthesis of (f)-Hirsutene
transition metal was quite reasonable,I8 the IR and NMR spectra,
as well as the analytical data, were rationalized cogently (but Sir:
clearly now speciously) in terms of the q3-silapropenyl complex
The recent years have experienced intense activity in the de-
la. The failure to observe the parent mass peak, however, is not velopment of synthetic routes to terpenoids possessing tricyclo-
too surprising in view of the propensity of carbonyl-metal com-
plexes to readily fragment in the mass spectrometer. Such [6.3.0.02,6]undecanering systems. Hirsutene ( l ) , coriolin, and
hirsutic acid present themselves as challenging targets in carbo-
fragmentation, characterized by the successive loss of C O mol-
cyclic synthesis as well as an exercise in the efficient introduction
ecules, often results in weak, if not absent, parent mass peaks.
All of the (vinylsi1ane)tetracarbonyliron complexes that we have of numerous oxygenated centers.
prepared to date are especially sensitive and fragment or decom- Considerable efforts have also been seen in the area of non-
linearly fused tricyclopentanoids such as isocomene and retigeranic
acid, both containing the tricycl0[6.3.0.0~~~]undecane ring system.’
(14) Complex 2a: n’6D 1.5269, doD1.5254. Reported for “la”: d6D In addition to the synthetic interest elicited by these terpenoids,
1.5065 (ref 2b). there exists an array of remarkable physiological properties as-
(15) The infrared spectrum of (ethy1ene)tetracarbonylironin the solid state sociated especially with the coriolin-type sequiterpenes.2 The
(thin film) also exhibits a weak absorption at 1317 cm-I: Andrews, D. C.;
Davidson, G. J . Organomet. Chem. 1972, 35, 162. antibiotic and antitumor activities of hirsutic acid and coriolin
(16) (a) Complex 2a (Beckman Model 25): , , ,A (hexane) 270 (sh) (c dictate an efficient synthetic approach to these compounds,
8800), 236 (sh) (14700), 212 nm (23 300). Reported for “la”: , ,A (hexane) particularly in view of their uncertain supply from natural sources.3
270 (sh) (e 7000[7700]), 236 (sh) (12600[13800]), 221 (sh) (17400[19000]),
212 nm (20500[22400]). Values in brackets are corrected extinction coef- Several interesting syntheses have appeared to date, describing
ficients, assuming a Fe(CO), rather than a Fe(CO), species; agreement is the preparation of hirsutic acid,4 coriolin,5 and their biogenic
within 5%. (b) For comparison, complex 2c: ,A, (hexane) 262 (sh) ( c SOOO), precursor, hirsutene.6
215 nm (27000). (c) The absorbance at 221 nm corresponds to c 18600,
consistent with the notion that there is a similar absorption at 221 nm for 221,
but because of poor resolution, it is not observed as a shoulder. On the other
hand, first-derivative analysis of the UV spectrum does not reveal a shoulder. (1) For recent synthetic efforts in this area, see: Paquette, L. A,; Han, Y .
(17) (a) Reported for “la” (ref 2): MS, m / e (re1 intensity) 298 (2.9), 270 K. J . Org. Chem. 1979,44,4016. Pirrung, M. C. J . Am. Chem. SOC.1979,
(4.9), 242 (6.8). 214 (21.6), 158 (23.9), 143 (21.0), 8 5 (54.4), 73 (100). 101, 7130. Oppolzer, W.; Battig, K.; Hudlicky, T. Helu. Chim. Acta 1979,
Complex 2% MS, m / e (re1 intensity) 326 (12.8), 298 (9.9), 270 (36.1), 242 62, 1493.
(48.9), 214 (73.0). 158 (30.5), 143 (39.7), 85 (87.2), 73 (100). (b) The (2) For a concise list of references pertaining to the biological activities,
observation of mass peaks at m / e 31 1 (3.5) and 253 (3.5), corresponding to see: Little, R. D.; Muller, G. W. J . Am. Chem. SOC.1979, 101, 7129.
P-CH3 and P-Si(CH3),, respectively, as well as peaks corresponding to the (3) Lansbury, P. T.; Wang, N. Y.;Rhodes, J. E. Tetrahedron Lett. 1979,
successive loss of C O from these fragments, also indicates a tetracarbonyliron 1829. Comer, F. W.; McCapra, F.; Quershi, I. H.; Scott, A. I. Tetrahedron
species. 1967, 23, 4761.
(18) Sakurai and co-workers had earlier demonstrated the interesting (4) Trost, B. M.; Shuey, C. D.; DiNimo, F., Jr.; McElvain, S. S. J . Am.
palladium-catalyzed addition of alkynes across a Si-Si bond: Sakurai, H.; Chem. SOC.1979, 101, 1284.
Kamiyama, Y . ;Nakadiara, Y . J . Am. Chem. SOC.1975, 97, 931. (5) Danishefsky, S.; Zamboni, R.; Kahn, M.; Etheredge, S. J. J . Am.
(19) West, R. J . Organomet. Chem. 1965, 3, 314. Chem. SOC.1980, 102, 2097.

0002-7863/80/1502-6351 $Ol.OO/O 0 1980 American Chemical Society

6352 J. A m . Chem. SOC.,Vol. 102, No. 20, 1980 Communications to the Editor
Scheme I (vinylmagnesium bromide in tetrahydrofuran, 0 "C). The dienyl
R unit in 4 could be introduced via the Claisen rearrangement of
an ortho ester, in analogy with the simple case of 1,4-penta-
dien-3-o1.* The inertness of the ring double bond in such rear-
rangements has been demonstrated by Bangel and Cresson.I3 The
use of triethyl orthoacetate as reagent and solvent (25 mL for each
g of alcohol, 1:lO ethyl ester), which was not isolated but hy-

/ drolyzed, led directly to 4 (20% KOH, reflux, 2 h) in 82% yield

from 3. (It proved crucial to wash the crude ester reaction mixture
with 3 N HCl to remove excess orthoacetate. Omission of this
i i , iii wash or attempts to remove orthoacetate by careful distillation
resulted in loss of material and yields of 20-40%.) The acid 4
L O O H [bp 110-1 15 OC (0.1 mmHg, Kugelrohr)] proved to be a single
bH isomer as evidenced by IH and I3C N M R spectra.12 Refluxing
3

i 4 iv, v 4 in a 2: 1 hexane/oxalyl chloride mixture for 1 h gave the acid

chloride (IR 1800 cm-I), which was immediately converted to ethyl
diazo ketone 5 (89% from 4) by adding the neat acid chloride to
a 0.3 M solution of diazoethaneI4 in ether. Any deviation in
concentration led to the production of an undesired a-chloro
ketone!15 In accord with our previous experience regarding the
cyclopropanation,* 5 gave vinylcyclopropane 6 stereospecifically
in 94% yield [Cu(acac),, refluxing benzene, 8 h]. A detailed
spectral analysis failed to show any isomeric material.
The crucial rearrangement of 6 to the cyclopentene 7 was
performed by evaporating a sample of 6 through a lead carbonate
conditioned, horizontally placed hot tube at 0.1 mmHg.9,16
Although model studies performed on terminally substituted dienes
gave mixtures of isomeric bicyclooctanes: with regard to the
I viii
substituent at C-8, it was envisioned that the energetics of cis,
anti, cis vs. cis, syn, cis ring junctions in 7 will be favorable in
the direction of the desired product. Indeed, the crude condensate
obtained from the pyrolysis of 6 was shown to contain 68% of 7,
22% of a fragmentation product (shown to be a bicyclic dienone)?
A H and 10% of isomeric tricyclic ketone 7a. This compound, as well
9 hirsutene, 1
as the ketone 7, was readily isomerized by RhCI3 in aqueous
a (i) CH,=CHMgBr/THF/O "C, (ii) CH,C(OEt),/Hg(OAc),/ ethanol" (reflux, 30 min) to 8, which was hydrogenated (PtO,,
CH,CH,CO,H, (iii) KOH/H,O, (iv) (COCl),/hexane, 40 psi, 8 h) to a known degradation product of hirsutene, norketone
(v) CH,CHN,, (vi) Cu(acac),/benzene/A, (Vii) 580 'C, PbCO, 9.6
coated glass, (viii) H,/F'tO,, (ix) CH,P'(Ph),I-/n-BuLi/Et,O,
(x) RhCI,/EtOH/A.
(12) All new compounds gave spectral and analytical data consistent with
their structures. Spectral data of the pertinent intermediates are tabulated
We have been investigating a new method of cyclopentene below. Infrared spectra were obtained on Pye-Unicam 3-300 and Perkin
annulation' based on the intramolecular cyclopropanation-rear- Elmer Model 257 instruments. IH and I3C N M R spectra were recorded on
Varian T-60 or HR-220 and Varian CFT-20 spectrometers, respectively, with
rangement of dienic diazo ketone^.^.^ We now report a direct (CH3)$i as internal standard. 3: IR (neat) 3380, 1640 cm-l; IH N M R
application of this methodology to the synthesis of hirsutene (1). (CDCI,) 6 1.05 (s, 6 H), 2.1 (br s, 4 H), 3.4 (s, 1 H, hydroxyl), 4.5 (d, 1 H,
J = 6 Hz), 5 . s 5 . 9 (m,4 H); "C NMR (CDC13) 6 29.8 (q, 2 methyl groups),
The synthesis is divisible into three major tasks: (a) preparation 38.4 (t), 47.5 (t), 48.4 (s), 72.4 (d), 114.7 (t), 124.0 (d), 139.2 (d), 144.2 (s).
of dienic acid 4, (b) ring closure and rearrangement to furnish 4: IR (neat) 3200-2800, 1705 cm-'; 'H N M R (CDCI3) 6 1.06 (s, 6 H), 2.1
tricyclic ketone 7, and (c) final transformation of 7 to hirsutene (br s.
~~~ ~,4 H).~ ~
~ 2.4 ,(br, s. 4 H). 5.6 (s. 1 HL 5.65 (br s. 1 H). 6.38 (d. 1 H. J =
~~~ ~~

via the known norketone 9.6 16 HZ); i3c NMR ( c ~ c i , ' )6 27.8 (t),'io.i ti), 34.0 (tj; 38.3 (si, 48.0 (t),
48.6 (t), 127.7 (d), 128.0 (d), 128.7 (d), 140.9 (s), 179.7 (s). 5: IR (neat)
We have chosen as our starting point the cyclopentenylaldehyde 2060, 1640, 1620 cm-'; 'H N M R (CDC13) 6 1.04 (s, 6 H), 2.08 (s, 3 H), 2.4
2, a popular compound in the field of coriolin and illudane terpenes (br s, 4 H), 2.7 (br s, 4 H), 5.6 (br s, 1 H), 5.65 (s, 1 H ) , 6.35 (d, 1 H, J =
16 Hz); "C N M R (CDCI,) 6 8.2 (q), 27.8 (t), 30.0 (q), 37.6 (t), 38.2 (s),
(Scheme I). Although the preparation of 2 is not trivial, an overall 46.5 (t), 47.9 (t), 61.9 (s), 127.8 (d), 128.3 (d), 128.5 (d), 140.9 (s), 193.6
yield of 64-70% is achieved by using the procedure either of (s). 6: IR (neat) 1716, 1630 cm-l; ' H N M R (CDCI,) 6 1.04 (s, 3 H), 1.07
Wilson and Turnerlo or of Magnusson and Thoren." (s, 3 H), 1.10 (s, 3 H), 1.85 (s, 1 H), 2.1 (br s, 5 H ) , 2.4 (d, 4 H, J N 3 Hz),
5.4 (s, 1 H); I3C NMR (CDCI,) 6 8.7 (q), 21.8 (t), 29.9 (q), 30.8 (d), 31.9
Aldehyde 2 was converted to vinyl carbinol 312 in 91% yield (t). 32.4 (d), 38.4 (s), 39.7 (s), 47.6 (t), 51.2 (t), 126.2 (d), 137.8 (s), 215.9
(s); mass spectrum (70 eV), m / e (%base peak) 204 (M'). 189 (62), 147 (39),
133 (29), 106 (50), 104 (85), 95 (43), 91 (B), 77 (42). 7: IR (neat) 1738,
1660 cm-'; 'H N M R (CDC13) 6 1.01 (s, 3 H), 1.05 (s, 3 H), 1.10 (s, 3 H ) ,
(6) Recent syntheses of hirsutene: Tatsuta, K.; Akimoto, K.; Kinoshita, 1.4-2.2 (m. 8 H), 2.8-3.4 (m, 2 H), 4.9 (s, 1 H); 13C N M R (CDC1,) 6 21.2
M. J. Am. Chem. SOC.1979,101, 61 16. Ohfune, Y.; Shirahama, H.; Mat- (9). 24.0 (t), 30.1 (9). 30.6 (q), 38.9 (t), 39.9 (t), 41.2 (t), 42.5 (s), 56.9 (s),
sumoto, T. Tetrahedron Left. 1976, 2795. Nozoe, s.;Furukawa, J.; Sankawa, 60.2 (d), 61.7 (d), 139.8 (d), 153.5 (s), 223.5 (s).
U.; Shibata, S . Ibid. 1976, 195. (13) Bangel, S.;Cresson, P. C. R. Hebd. Seances Acad. Sci., Ser. C 1969,
268, 1535.
(7) For the latest intramolecular cyclopentane annulation procedure and (14) Marshall, J. A.; Partridge, J. J. J . Org. Chem. 1968, 33, 4094.
for the literature review, see: Jacobson, R. M.; Lahm, G. P.; Clader, J. W. ( I 5 ) The best results were obtained when 0.513 g of nitrosoethylurea was
J . Org. Chem. 1980, 45, 395. added to 1.3 mL of 50% KOH and 6 mL of Et,O, at 0 OC. After the
(8) Hudlicky, T.; Sheth, J. P.; Gee, V.; Barnvos, D. Tetrahedron L e f t . generation of diazoethane was complete, the ethereal layer was decanted and
1979, 4889. Hudlicky, T.; Sheth, J. P. Ibid. 1979, 2667. Hudlicky, T.; dried with KOH pellets. An aliquot of 4 mL of Et,O was used to wash the
Kutchan, T. M. Ibid. 1980, 691. aqueous layer. The solution thus obtained was -0.3 M in diazoethane
(9) Hudlicky, T.; Koszyk, F. J. Teirahedron Lett. 1980, 2487. Hudlicky, (suitable for 1 mmol of acid chloride).
T.; Koszyk, F. J.; Kutchan, T. M.; Sheth, J. P. J. Org. Chem., submitted for (16) The use of PbC0, conditioning minimizes the competing processes.
publication (full paper with experimental details for all new compounds). A slurry of PbC03 in H 2 0 is poured through the column, and the column is
dried at 300 OC prior to pyrolyses.
( I O ) Wilson, S. R.; Turner, R. B. J . Org. Chem. 1973, 38, 2870. (17) Andrieux, J.; Barton, D. H. R.; Patin, H. J . Chem. Soc., Perkin Trans
(11) Magnusson, G.; Thoren, S. J . Org. Chem. 1973, 38, 1380. 1 1977, 359
 J . A m . Chem. Sot. 1980, 102, 6353-6355 6353

Careful medium-pressure liquid chromatography [silica gel, Scheme I

CH2Cl2,hexane (9:1)], furnished pure analytical samples of 7 and
7a. Their I3C N M R spectra, as well as the comparison of the
IR spectra of their hydrogenation products with those of authentic
9,6served as final structure proofs. Norketone 9 was converted
to hirsutene 1 according to an already published procedure.6
The described synthesis proves rewarding in the following ways.
First, it marks an easy access to the coriolin class of sesquiterpenes
by having served as a model study for the production of the more
complicated systems. Several approaches to the oxygenated co-
riolin nucleus are presently being tested in our laboratory. Second, hypertrophic growth of potato tuber tissue, were reported pre-
it ascertains the utility of intramolecular carbenoid addition to viously. While the synthesis of (f)-coronafacic acid (2), the acidic
1,3-dienes as a new method for internal cyclopentane annulation. component of coronatine, has been ~ o m p l e t e dno
, ~ satisfactory
Third, it should be borne in mind that the present approach results were obtained for the control of its stereochemistry. In
furnishes hirsutene in 37% overall yieldI8 from aldehyde 2 (23% order to solve the problem, we utilized an intramolecular Diels-
from dimedone), without the use of chromatography, in a single Alder reaction between &!?-diene and enone moieties (a) to
step (except in the preparation of analytical samples); this last produce favorable stereochemistry at Cja and C6 in 2 (Scheme
criterion makes our approach to the coriolin skeleton attractive I). Though a number of intramolecular Diels-Alder reactions
from a practical point of view. have been applied to the synthesis of natural products," difficulties
The synthetic studies of oxygenated coriolins and approaches have always arisen in the construction of the labile diene and
to the tricycl0[6.3.0.0~~~]undecane subunit of retigeranic acid are dienophile moieties. This communication describes a new ste-
the points of current interest in our laboratory. reoselective synthesis of (f)-coronafacic acid through thermal
reaction of latent dienedienophile moieties (b) which are masked
Acknowledgment. We thank the donors of the Petroleum as an equally, thermally labile cyclobutene (c) and methyl ketone
Research Fund, administered by the America1 Chemical Society, Diels-Alder product (d), readily derived from trivial compounds
and the Department of Chemistry at Illinois Institute of Tech- as shown by retrosynthesis.
nology for support of this work. Thanks are extended to Professor Condensation of the enamine from n-butanal and dimethyl-
K. Tatsuta of Keio University, Japan, for providing us with the amine with diethyl maleate, quaternization with p-TsOMe, and
spectra of hirsutene and norketone. The use of mass spectral subsequent elimination yielded known diester 35,6(63% yield from
facilities and a high-field NMR spectrometer at Indiana University the enamine) (Scheme 11). The stereochemistry of diester 3 was
is gratefully appreciated.
Note Added in Proof: After the submission of this manuscript (2) (a) Ichihara, A.; Shiraishi, K.; Sakamura, S.; Nishiyama, K.; Sakai,
the authors became aware of two very elegant syntheses of hir- R. Tetrahedron Lett. 1977, 269. (b) Ichihara, A,; Shiraishi, K.; Sakamura,
sutene: one published by A. E. Greene, Tetrahedron Lett. 1980, S.; Furusaki, A,; Hashiba, N.; Matsumoto, T. Ibid. 1979, 365.
(3) Ichihara, A,; Kimura, R.; Moriyasu, K.; Sakamura, S . Tetrahedron
3059; the other forthcoming by Little, R. D., et al. Lett. 1977, 4331.
(4) (a) Oppolzer, W. Angew. Chem., Int. Ed. Engl. 1977, 16, 10; Ibid.
1978, 17, 793. (b) Kametani, T.; Fukumoto, K. Heterocycles 1977, 8, 456.
(18) The entire synthesis was repeated three times to ascertain reproduc- (c) Wilson, S. R.; Mao, D. T. J . A m . Chem. SOC.1978,100,6289. (d) Taber,
ibility and to obtain sufficient materials for I3C N M R analysis. D. F.; G u m , B. P. Ibid. 1979, 101, 3992.
( 5 ) Brannock, K. C.; Bell, A. B.; Burpitt, R. D.; Kelly, C. A. J . Org. Chem.
Tomas Hudlicky,* Toni M. Kutchan 1964, 29, 801.
Department of Chemistry, Illinois Institute of Technology (6) Spectral and analytical data for all new compounds are as follows. 3:
IR (neat) 1730, 1620 cm-'; N M R (90 MHz, CDCl,) 6 1.00 (3 H , t, J = 7
Chicago, Illinois 60616 Hz), 1.22 (3 H, t, J = 7 Hz), 1.24 (3 H, t, J = 7 Hz), 1.62 (2 H, q, J = 7
Hz), 2.20 (1 H, dt, J = 7, 1.5 Hz), 3.20 (1 H, d, J = 1.5 Hz), 4.10 (2 H, q,
Stephen R. Wilson, David T. Mao J = 7 Hz), 4.15 (2 H, q, J = 7 Hz), 6.85 (1 H, s); M, calcd for CI2Hl8O4
Department of Chemistry, Indiana University 226.1205, found 226.1242. 4: IR (neat) 3350, 1010 cm"; N M R (90 MHz,
CDCIJ 6 0.90 (3 H, t, J = 7 Hz), 1.50 (2 H, q, J = 7 Hz), 2.20 (1 H , t, J
Bloomington, Indiana 47405 = 7 Hz), 2.60 (1 H , dd, J = 5 , 9 Hz), 3.48 (1 H, t, J = 9 Hz), 3.82 (1 H,
Received April 7, I980 dd, J = 5,9 Hz), 4.05 (2 H, s), 6.00 (1 H, s); M, calcd for C 8 H I 4 o 2142.0992,
found 142.0964. Anal. (C8H1402)C, H ; C calcd, 67.57; found, 68.04. 5:
IR (neat) 3400, 1680 cm-'; N M R (90 MHz, CDC1,) 6 1.00 (3 H, t, J = 7
Hz), 1.65 (2 H, q. J = 7 Hz), 2.50 (1 H, t, J = 7 Hz), 2.90 (1 H, m), 3.85
(1 H, dd, J = 6, 9 Hz), 7.10 (1 H, d, J = 2 Hz), 9.00 (1 H, s); M, calcd for
Synthesis of (f)-Coronafacic Acid. Efficient C8HI202 140.0836, found 140.0826. 6: IR (neat) 3450, 1080 cm-I; N M R
Intramolecular Diels-Alder Reaction of Latent (90 MHz, CCI4) 6 0.95 (3 H, t, J = 7 Hz), 1.55 (2 H , q, J = 7 Hz), 2.25 (1
Diene-Dienophile Functionality via Thermal Reaction H,t,J=7Hz),2.60(2H,m),3.55(2H,m),3.95(4H,m),5.15(1H,s),
6.20 (1 H, s); M, calcd for CI0Hl6O3184.1097, found 184.1089. 7 IR (neat)
2750, 1720, 1090 cm-'; NMR (90 MHz, C C 4 ) 6 1.00 (3 H, t, J = 7 Hz), 1.60
Sir: (2 H, q, J = 7 Hz), 2.25 (1 H, t, J = 7 Hz), 3.00 (1 H, d, J = 4.5 Hz), 3.85
The structure' and stereochemistry* of coronatine ( l ) ,which (4 H , s), 5.22 (1 H, s), 6.40 (1 H, s), 9.00 (1 H, d, J = 4.5 Hz); M, calcd
induces phytotoxic lesions on the leaves of Italian ryegrass and for CI0Hl4O3182.0942, found 182.0941. 8: IR (neat) 1710 cm-'; N M R (90
MHz, CC14) 6 1.54 (3 H, s), 1.56 (3 H, s), 2.05 (3 H, s), 1.20-2.90 (3 H, m),
3.20 (1 H, m), 3.40 (1 H, m), 6.20 (2 H, m); M,calcd for C12H160176.1201,
found 176.1214. 9: IR (neat) 3450, 1700 cm-I; N M R (90 MHz, CDC13) 6
0.95 (3 H, t, J = 7 Hz), 1.60 (6 H, s), 1.40-2.00 (3 H, m), 2.20 (1 H, m),
2.40-2.70 (3 H, m), 2.20 (1 H , m), 3.00 (1 H, m), 3.30 (1 H , m), 3.60 (1 H,
m), 3.90 ( 5 H, m), 5.20 (1 H, m). 6.30 (1 H, m), 6.40 (2 H, m); M, calcd
for C22H3004 358.2142, found 358.2140. 10: IR (neat) 1690, 1670, 1620
cm-]; N M R (90 MHz, CCI4) 6 1.00 (3 H, t, J = 7 Hz), 1.60 (6 H , s),
1.25-2.10(3H,m),2.50(1H,m),3.15(1 H , d , J = 8 H z ) , 3 . 3 5 , 3 . 4 5 ( e a c h
1 H, m), 4.00 (4 H , m). 6.20 (1 H, d, J = 16 Hz), 6.30 (3 H, br s), 6.85 (1
H, dd, J = 8, 16 Hz); M, calcd for C22H2803 340.2037, found 340.2026. 11:
IR (neat) 1710, 1090 cm-l; NMR (90 MHz, CC14) 6 0.95 (3 H, t, J = 7 Hz),
1.55, 1.60 (each 3 H, s), 1.10-2.60 (11 H, m), 3.40, 3.50 (each 1 H, m), 3.90
1 (4 H, m), 5.20 (1 H, s), 6.15 (1 H, s), 6.25 (2 H, m). Anal. (C22H3003) C,
h H. 12: IR (KBr) 1740 cm-l; N M R (90 MHz, CCI4) 6 0.95 (3 H , t, J = 7
Hz), 1.15-2.90 (11 H, m), 3.80 (4 H, m), 5.00 (1 H, s), 5.65 (1 H, br s).
~~ ~

Anal. (CI4H2,O3)C, H. 2: IR (KBr) 2950, 1740, 1680, 1620 cm-'; IR

(1) Ichihara, A.; Shiraishi, K , Sato, H.; Sakamura, S.; Nishiyama, K.; (CHCI,) 3100, 1735, 1680, 1630 cm-l; N M R 6 0.95 (3 H, t, J = 7 Hz), 3.00
Sakai, R.; Furusaki, A.; Matsumoto, T. J . A m . Chem. SOC.1977, 99, 636. (1 H, m), 6.95 (1 H, br s). Anal. (CI2Hl6O3)C, H.

0002-7863 /80/ 1502-6353$01 .OO/O 62 1980 American Chemical Societv