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tion of 2,3-dimethyl-2-butene further confirmed its identity tion of the rings A and C in 13 could be confirmed by an

as lo2. X-ray structure analysis.

After correction for differing sensitizer optical densities,
the maximum intensities of 1- and 2-sensitized '02lumi-
nescence were compared. Since the quantum yield of tri-
plet formation from 2 is 0.81[51,and this state is efficiently
quenched by oxygen to form 'Oz[51, the absolute quantum
yield of cercosporin-sensitized formation of 'Oz could be
determined. Based on four independent determinations,
the relative ratio of luminescence produced from 2 to that

produced from 1 was found to be 1.01f0.04. Two sepa-
rate determinations of the relative rates of photooxygena-
tion of 2-methyl-2-pentene in benzene sensitized by 2 and
1 gave the ratio 1.00-+0.12. Both ratios indicate that the H
quantum yield of formation of '02 sensitized by 1 is
0.81 f 0.07.
This large quantum yield strongly supports the sugges-
tion that singlet oxygen is the toxic agent in host plants.
This is a striking example of the use of a chemical mecha-
nism by a parasite to gain an "environmental advantage". +
Received: April 26, 1983;
revised: July 12, 1983 [Z 358 IE]
German version: Angew. Chem. 95 (1983) 729 U

111 S. Yamazaki, T. Ogawa, Agr. Biol. Chem. 36 (1972) 1707; R. J. J. C. Lons-

berg, U. Weiss, C. A. Salemink, A. Amone, L. Merlini, G. Nasini, Chem.
Commun. 1971, 1463.
121 M. E. Daub, Plan$ Physiol. 69 (1982) 1361. 9
[3] a) M. E. Daub, Phytoparhology 72 (1982) 370; b) M. E. Daub, personal
[4] a) P. R. Ogilby, C. S. Foote, J. Am. Chem. Sac. 104 (1982) 2069; b) ibid.
IOS (1983) 3423.
[S] R. Bonnett, A. A. Charalambides, E. J. Land, R. S. Sinclair, D. Tait, T. G.
Truscott, 3. Chem. Soc. Farad. Trans. I 76 (1980) 852. . H
[6] Cercosporin was provided by Dr. M.E. Daub, Michigan State University.
Its structure and purity were confirmed by comparison of the absorption
and NMR spectra with published data"'. 2-Methyl-2-pentene (Aldrich) J p Hl O
was purified by column chromatography on basic A1203.C6H6(Mallinc-
krodt) was distilled from P20, immediately before use. 2 (Sigma) and 0 0
C6H6(Cambridge Isotope Laboratories) were used as received.-The ap-
paratus used to observe '02 luminescence has been described previously
L 10 I 11

Synthesis and Structure of a Linearly anti-Annelated

Tetracycloundecane. A Potential Precursor for a H
Coriolin Synthesis i
By Martin Demuth*, Antonio Canovas, Eva Weigt, L
Carl Kriiger, and Yi-Hung Tsay
Dedicated to Professor Giinther 0. Schenck on the 12
occasion of his 70th birthday
We recently presented a widely applicable concept for Scheme 1. a: NaH, Mel, tetrahydrofuran, SO "C. b: 3-chloro-2-methylpro-
pene, KBr, tBuOK, tBuOH, toluene, 80C. c: Os04, NalO.,, dioxane, HZO,
the synthesis of cyclopentanoid natural products based on
room temperature. d: Nafion-TMS (perfluorinated trimethylsilyl sulfonate
the utilization of tricyclo[]octan-3-one
1 as central resin), toluene, 80C. e: AcOAg, 12, toluene, room temperature. f: 1.5-diaza-
optically active building block"*21.Scheme 1 outlines the bicyclo[4.3.0]non-5-ene, toluene, room temperature. g: tBuOK, tBuOH, to-
strategy (AB + C principle) now chosen by us for the pre- luene, 8 0 T , 5 min. h: as g but 12 h or TosOH cat., CH,OH, room tempera-
ture. i: iodotrimethylsilane, CHZCI2,room temperature. The numbering in
paration of the tetracycloundecanes 9 and 12, which are 10-13 is that generally employed in coriolin chemistry.
potential precursors for the synthesis of coriolins"'. The
most important step in the sequence involves the pre-
viously only indirectly dernon~trated~~'anti-annelation of a The alkylation 2 + 3 proceeds in 86% yield and just as
third five-membered ring to 1. The desired anti-configura- selectively as the preceding methylation 1 + 2[2'31.Oxida-
tive degradation (3+4 ; 82%) and subsequent isomeriza-
tion 4+5 (60Y0)'~'afforded a suitable starting material for
[*I Dr. M. Demuth, Dr. A. Cbnovas, E. Weigt further functionalization of ring A. The Prkvost addition of
Max-Planck-Institut fur Strahlenchemie
Stiftstrasse 34-36, D-4330 Mulheim a. d. Ruhr (Germany)
acetyl hypoiodate to the double bond of 5 yields 6 and 7
Prof. Dr. C. W g e r , Dr. Y.-H. Tsay (X-ray structure analysis)
with equally high selectivity (10 : 1) as has already been ob-
Max-Planck-Institut fur Kohlenforschung served in an analogous case[',31.After re-formation of the
Kaiser-Wilhelm-Platz 1, D-4330 Mulheim a. d. Ruhr (Germany) three-membered ring (6-8; 77%, annelation of the ring C

Angew. Chem. In!. Ed. Engl. 22 (1983) No. 9 0 Veriag Chemie GmbH, 6940 Weinheim, 1983 0570-0833/83/0909-0721 $02.50/0 72 1
(8+9, 11) was achieved with potassium tert-butoxide in Synthesis and Structure Determination of
fert-butyl alcohol and toluene at 80C. Interruption of this I(PEtWGB~Hm1~-
reaction after 5 min permitted isolation of the primary al- A Binuclear Rhodacarborane Containing
do1 product 9 ; the end product after 12 h was the penta- Four Bonds Between Two Icosahedra**
cyclic ether 11 (93%). The labile primary product 9 readily
By Paul E. Behnken, Carolyn B. Knobler, and
cyclizes to 11 in the presence of traces of bases or acids,
M . Frederick Hawthorne*
the presumed intermediary enone 10 not being detectable
(for model considerations cf. [l]). Since 9 and 10 proved to In the course of our studies of the homogeneous cataly-
be of no synthetic value we searched for a stable derivative sis of olefin hydrogenation by closo-3,3-(PPh3),-3-(H)-
having basically similar features and which is readily ac- 3,1,2-RhC2B9Hl, 1[11,we characterized and reported the
cessible from 11. To avoid the undesired internal ether for- molecular structure of [(PPh3)RhC2B9H,l]22[*l,a binuclear
mation, it seemed desirable that ClO be either exo-substi- (ph0sphane)rhodacarborane complex formed by formal
tuted with oxygen or bear a readily modifiable group not loss of H2 and two phosphane ligands from two molecules
containing oxygen. The latter variant could be achieved by of 1. Of interest were the Rh-H-B interactions support-
treatment of 11 with iodotrimethylsilane (TMSI)IS1;this af- ing the Rh-Rh bond and the stereospecificity of their for-
forded the crystalline diiodo compound 13 as major prod- mation. The two terminal B-H bonds involved in the
uct (64%) (Fig. 1). Re-formation of the three-membered Rh-H-B interactions determine a specific stereoisomer:
of the six possibilities only 2 is observed with both enan-
tiomers present in the unit cell.
n A
In an attempt to further probe the nature of these inter-
actions, cyclooctadiene(triethy1phosphane)rhod-
ium(i) chloride was allowed to react with Cs2[7-(7'-7',8'-
C2B9H11)-7,8-C2B9H11] 3[31(15 h reflux) to produce a dark
blue compound 4 in 16% yield.

Fig. 1. Structure of the diiodo compound 13 in the crystal. a=7.789(1),

b= 13.7733): c = 14.293(1) A, n=64.51(1), 8=89.353(7), y=73.98(1)',
V = 1319.90 A,p,,,=2.154 g ~ m - MoKa,g=46.9
~ , cm-', Z = 4 , space group Crystals of 4 (Fig. 1) contain two icosahedral rhodacar-
Pi, 5960 reflections, 5010 observed (20), 271 refined parameters, R=0.0565, borane fragments joined symmetrically at three vertices.
R, =0.696. Further details of the crystal structure investigation are obtain- Carbon atoms C1 and C1' are covalently bonded as in the
able on request from the Fachinformationszentrum Energie Physik Mathemat-
ik, D-7154 Eggenstein-Leopoldshafen by quoting the depository number
CSD 50466, the names of the authors, and full citation of the journal.

ring (-+ 12 ; 72%) was accomplished by reaction of 13 with

diazabicyclo[4.3.0]non-5-ene; thus a stable anti-annelated
tetracycloundecane with appropriate ring A substitution
was prepared for the first time. As initial step of the ring-
opening 11 + 13 we postulate cleavage of the ether by SN2
substitution with iodide at C10 and concomitant formation
of the enone (-+12). The opening of the cyclopropane ring
of 12 taking place in the second step does not occur at
C11, but, because of steric interaction with the 10-exo iod-
ide, selectively at C1. As has also been found in other ex-
amples, the iodide addition at C1 occurs with inversionI41.

Received: May 25, 1983 [Z 395 IE]

German version: Angew. Chem. 95 (1983) 747
The complete manuscript of this communication appears in:
Angew. Chem. Suppl. 1983, 1053-1065 W
Fig. 1. ORTEP projection of the binuclear rhodium complex
[(Et,P)RhC2BPHl0j24. H atoms other than those involved in bridging are om-
itted for clarity. For details of the crystal structure analysis (R,=0.036), see
[I] M. Demuth, K. Schaffner, Angew. Chem. 94 (1982) 809; Angew. Chem. Supplement.
Inr. Ed. Engl. 21 (1982) 820.
[2] M. Demuth, S. Chandrasekhar, K. Schaffner, J . Am. Chem. Soc., in
press. [*I Prof. M. F. Hawthorne, P. E. Behnken, Dr. C . B. Knobler
131 M. Demuth, S. Chandrasekhar, K. Nakano, P. R. Raghavan, K. Schaff- Department of Chemistry and Biochemistry,
ner, Helu. Chim. Acta 63 (1980) 2440. University of California
141 M. Demuth, G. Mikhail, Tetrahedron 39 (1983) 991. Los Angeles, CA 90024 (USA)
151 Review: G. A. Olah, S . C. Narang, Terrahedron 38 (1982) 2225. [**I This work was supported by the U. S . National Science Foundation.

122 0 Verlag Chemie GmbH, 6940 Weinheim, 1983 0570-0833/83/0909-0722 $02.50/0 Angew. Chem. inr. Ed. Engl. 22 (1983) No. 9