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Indole Pigments from the Fruiting Bodies of the Slime Mold Arcyria denudata.

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nedicarboxaldehydelto1.On treatment with LiAlH, in ether
at 35 "C, (10) is reduced to (4).
[lo] H. Musso, private communlcation; W Trautmann, Dissertation. Universitat
Karlsruhe 1976.
Ill] M. Chrisfl, Chem. Ber. 108, 2781 (1975).
1121 M. Chrisrl, R. Herbert, Org. Magn. Reson. 12. 150 (1979).
Table 1. Some physical data of the compounds /2), (3). (5)-(8) and (10) (NMR
spectra in CDCI,, in the case of (10) in C6D6, 6 values).
(21, b.p. 4f-50"C
(bath)/O.Ol torr; 'H-NMR: 2.05 (I, I-H, 7-H,
J12%Jth%J27=Jfi.7=2.8Hz), 2.38-2.67 (m. 2-H, 6-H). 3.39 (dd, 5-H,rnn%,
Js.s= 10.7, J s r
6 ~ 3 . 0Hz), 3.75 (d, 5-H<,J, 3.94 (d. OH. J o ~ . , = 6 . 0Hz), 4.92
(dd. 3-H, J2.3=2.7 Hz); "C-NMR: 4.0 and 4.4 (in each case d 207 Hz, C-1 and
C-7), 37.2 (d 156.6 Hz. C-6). 43.1 (d 158.9 Hz. C-2). 55.8 (t 144.9 Hz, C-5). 85.8
(d 165.5 Hz, C-3)
13). b.p. 78'C/0.05 tom; 'H-NMR: 1.65 (1, I-H, 3-H, J,.2=4.0 Hz). 2.91 (m, 2-H,
Hz);
4-H). 3.58 (pseudo-1, CH2, line sepn. ca. 5 Hz), 4.67 (1, OH, JoH.CH2=5.0
"C-NMR: 11.4 (d 197.3 Hz. C-1, C-3), 55.8 (d 147.4 Hz. C-2. C-4). 63.3 (t, 142.7
Hz. C H d
0).b.p.72"C/0.05 torr; 'H-NMR: 1.90(m, lH),2.1-2.4(m.3H).3.87(br.s,3H. 4-H), 4-12 (br. S. OH); "C-NMR: 0.1 and 2.4 (in each case d 215.5. 217.7 Hz,
C-1. C-6), 37.9 (d 168.4 Hz, C-2, C-5), 70.7 (d 153.7 Hz. C-3, C-4)
(6)- b.p. 25-35°C (bath)/O.Ol torr; 'H-NMR: (6a) [a] 1.56 (s. CCH,), 1.7-2.5
(m. 2-H. 5-H, 3-H. 4-H), 3.14 (s, OCH,), 4.57 (br. s, 1-H. 6-H); (66): 1.37 (s,
CCH,). 1.7-2.5 (m, 2-H, 5-H, 3-H, 4-H), 3.38 (s, OCH,). 4.45 (br. s, I-H, 6-H);
"C-NMR: (60): 2.8 (d 218.4 Hz, C 4 ) , 6.3 (d 217.3 Hz. C-3). 23.6 (q 128.0 Hz.
CCH,). 37.9 (d 169.8 Hz, C-2, '2-5); 48.9 (q 142.7 Hz, OCH,), 83.2 (d 160.3 Hz,
C-1, C-6). 126 2 ( S , C-8); (66): 4.2 (d 219.1 Hz, C-4). 6.9 (d 217 Hz, C-3). 23.8 (4
128.0 Hz, CCH,), 37.0 (d, 169.9 Hz, C-2, C-5). 50.1 (q 143.4 Hz. OCH,), 81.6 (d
158.1 Hz. C-1. C-6). 126.6 (s. C-8)
(71, b.p. 45-50°C (bath)/O.Ol torr; 'H-NMR: 2.06 (s, CH,). 2.38 and 2.46 (in
each case br. s, I-H. 6-H, 2-H. 5-H), 3.84 (br. s, 4-H). 4.86 (br. s, 3-H); ')C-NMR:
6.0 and 7.2 (in each cased 220.6 Hz, C-1, C-6). 20.9 (4. 129.4 Hz, CH,). 35.6 (d
172.8 Hz. C-2). 39.7 (d 173.6 Hz, C-5). 65.0 (d 160.3 Hz, C-4). 85.2 (d 161.0 Hz,
C-3). 170.4 ( s , C==O)
(8). b.p.40-6OoC(bath)/14torr; 'H-NMR: 2.19(dt,4-H, J,.4=8.1 Hz, J2.4=2.6
Hz), 2.33 (m, 2-H, 5-H). 2.98 (dt, 3-H, J2.,=1.1 Hz). 3.26 (s, I-H, 6-H); "CNMR: - 1.1 (d 221.8 Hz, C-4). 26.5 (d 214.7 Hz, C-3). 37.0 (d 170.6 Hz, C-2. C5). 56.9 (d 189.0 Hz, C-1, C-6)
(10). IR (ether): 1720 cm- ' (C=O); 'H-NMR: 1.48 (t. I-H. 3-H. J,.2=3.6 Hz),
2.81 (m, 2-H, 4-H), 9.15 (br. d, CH=O, line sepn. 2.4 Hz)
[a] (6a) major amount isomer, (66): minor amount isomer.
The structures of (2), (3), (S)-(8), and (10)are confirmed
by NMR spectra (Table 1). Two phenomena warrant special
comment: The value of 197.3 Hz for the direct CH coupling
of C-1, C-3 in (3) is relatively small, but by comparison with
known data["] can possibly be explained in terms of the dihedral angle being enlarged by the two endo substituents. In
(8) there is a large difference of 27.6 ppm between the chemical shifts of C-3 and C-4, indicating that the epoxide ring exerts a similar anisotropic effect as the cyclopropaneI","] and
aziridinel21rings.
(3) and (10)are the first bicyclo[l.l.0]butanes containing
no substituents other than two functional groups in the endo
positions.
Received: April 3. 1980 [Z 467 b IE]
German version: Angew. Chem. 92,466 (1980)
CAS Registry numbers:
( I ) , 659-85-8; (2). 73688-07-0; (3). 73688-08-1; (5). 73688-09-2; (6), isomer 1,
73688-10-5; (6). isomer 2, 73744-67-9; (7). 73688-1 1-6: (8). 73688-12-7; (9),
73688-13-8;
73688-14-9
111 Review: U. Burger, Chimia 33, 147 (1979); more recent works: R. Aumann,
H. Wormann, Chem. Ber. 112, 1233 (1979); R. J. Roth. Synth. Commun. 9,
751 (1979); R. Herbert. M. Christl, Chem. Ber. 112. 2012 (1979)
121 M. Chrisfl, H. Leinmger, Tetrahedron Lett. 1979. 1553.
131 M. Christl, G. Bnjntmp, Chem. Ber. 107, 3908 (1974); we now also carry out
the ozonolysis in ether.
[4] K. B. Sharpless, K. Akashi, J. Am. Chem. Soc. 98, 1986 (1976).
[5] P. Dansetfe, D. M. Jerina, J . Am. Chem. SOC.96, 1224 (1974); M. S. Newman, C. H. Chen. ibid. 95, 278 (1973).
[6] J. Rebek, R. McCready, S. WOE A . Mossman, J. Org. Chem. 44, 1485
(1979).
171 P. Bischof; R. Gleiter, E. Muller, Tetrahedron 32, 2769 (1976); P.J. Harman,
.
I
.
E. Kent, T. H. Con, J. 3. Peel, G. 1). Willef, J. Am. Chem. SOC.99, 943
(1977).
[81 Review: W. Adam, Adv. Heterocycl. Chem. 21,437 (1977).
[9] Values for bicyclo[l.l.Olbutane: J1.2px,,=2.9Hz and J,.2end,,=1.2 Hz; K.
Wuthrich, S. Meiboom, L. C. Snyder, J. Chem. Phys. 52, 230 (1970).
Angew. Chem. Int. Ed. Engl. 19 (1980) No. 6
Indole Pigments from the Fruiting Bodies of the
Slime Mold Arcyriu denudatd"'
By Wolfgang Steglich, Bert Steffan, Lothar Kopanski, and
Gerd Eckhardt"]
Dedicated io Professor Row Huisgen on the occasion of
his 60th birthday
Slime molds constitute a class of very primitive organisms
of uncertain systematic position which can be assigned neither to the plant nor the animal kingdom[']. Their delicate
fruiting bodies (Sporangia) often have bright colors, the
chemical nature of which still remains virtually unknown'''.
From 2 g of the red fruiting bodies of Arcyria denudata (L.)
Wettstein, we obtained a red methanolic extract, which was
separated by chromatography on Sephadex LH-20 (eluent
methanol) into three red and two yellow main fractions (see
Table 1).
Table 1. Pigments from Arcyria denudnta, purified by re-chromatography. Empirical formulas were determined by high-resolution mass spectrometry [a].
Arcyriarubin B
Arcyriarubin C
Arcyriaflavin B
Arcyriaflavin C
Arcyroxepin A
(1)
(2) [c]
(3)
(4)
(5) [c]
Rr [b]
Color
Yield
[XI
M.p.
I"C1
0.33
0.21
0.33
0.21
0.42
red
red
pale yellow [d]
pale yellow [d]
red [el
0.4
154-155
205-206
350
350
268-270
1.5
0.05
0.05
0.3
[a] It), CZOHI,N3O3;(21, C20HI,N,O4; (3). C X & ~ , , N A(4).
~ : CNH,,NXO~
(S),;
C20H,,N,0,. [b] Silica gel TLC plates, Merck 60 FZS4
(eluent: benzene/ethyl formate/formic acid 10: 5 : 3). [c] Correct elemental analyses obtained. [d] Strong
bright yellow fluorescence at 366 nm. [el Reversible color change to violet over
NH, vapor.
In its 'H- and I3C-NMR spectrum (Table 2) arcyriarubin
C shows only half of the full set of signals and must therefore
have a symmetrical structure. Accordins to the IR bands at
1755 and 1705 cm-' a maleimide i i i a b i \ . i ! is present; this is
confirmed by the 13C-NMR signals '11 c ) - 175.3 and 129.213].
From the splitting and position of the arene signals, and
from the NH protons (coupled with 2-H) at 6 = 10.42 in the
'H-NMR spectrum, it follows that the maleimide is substituted by two (5- or 6-hydroxy)indol-3-y1 groups. The I3CNMR spectrum would favor (2): the position of the C-7 signal at 6=97.7 can be reconciled only with the OH group being in a 6-positionI4l.
(1). R = H
(2), R = OH
I*]
(3). R = H
(4), R = OH
v
R
Prof. Dr. W. Steglich. Dip1.-Chem. B. Steffan, DipLChem. L. Kopanski, Dr.
G. Eckhardt
Institut fur Organische Chemie und Biochemie der Universitat
Gerhard-Domagk-Strasse 1, D-5300 Bonn (Germany)
I**] Fungal Pigments, Part 36. This work was supported by the Deutsche Forschungsgemeinschaft. We thank Prof. Dr. F. Oberwinkler, Tubingen, and Dr. H.
Neubert, Buhl/Baden, for identifying the species.-Part 35: H. Bed. A . Bresinsky,
L. Kopanski, W . Steglich, Z . Naturforsch. 33c, 820 (1978).
0 Verlag Chemie, GmbH, 6940 Weinheim, 1980
0570-0833/80/0606-459 S 02.50/0
459
Table 2. Spectroscopic data of the Arcyria pigments.
UV [nm) in CH,OH
IR [cm - ‘j in KBr
‘H-NMR [a1 in CD,COCD,
“C-NMR [b] in CDIOD
h,,,=465
( l o g f 3.77),
392 (sh, 3.57). 281
(3.93)
3440 br. s, 2960 m. 1760
m, 1715 s, 1630 w. 1538
(2)
A,,,=474
(logs 3.76).
283 (3.93)
3430 br. s, 1755 w. 1705
s, 1625 m, 1535 s
97.7 (C-7): 107.7 (C-3/3’): 110.8 (C-5): 112.3 (C7’); 120.7 (CH): 120.9 (C-3a): 122.7 (CH): 123.0
(CH); 123.2 (C-4): 127.3 (C-3a’); 128.9 (C-2/8’):
129.7 (C-2‘); 129.9 (C-8); 137 8 (C-7a‘); 138.9 (C7a): 154.5 (C-6). 175.3 (C-9/9’)
97.7 (C-7): 107.8 (C-3); 110.9 (C-5): 121.0 (C-3a):
123.3 (C-4); 128.7 (J= 190 Hz. C-2); 129.2 (C-8):
138 8 (C-7a); 1544 (C-6); 175.3 (C-9)
(3)
h,,,=414
(loge 3.19).
323 (4.11), 280 (3.79,
271 (3.70); 2.29 (4.07)
3420 br. s, 2955 s, 2880
m, 1750 w. 1705 s, 1620
br. m
6.24 (dd. J=8.7+2.1 Hz. 5-H); 6.72 (d, 8.7 Hz, 4H): 6.85 (d. 2.1 Hz. 7-H), 6.72-7.05 (m. 5’.6’,7’H): 7.42 (“d”,8 Hz. 4-H); 7.73 (d, 2.7 Hz. 2-H);
7.82 (d, 2.9 Hz. 2’-H); 9.63 (br. s, 10-NH): 10.52
(br. s, 1’-NH); 10.78 (br. s. I-NH)
6.27 (dd. J=8.4+2.2 Hz, 5S’-H). 6.79 (d, 8.4 Hz.
4.4-H); 6.85 (d. 2.2 Hz, 7,7’-H); 7.66 (d, 2.5 Hz.
2.2’-H): 9.51 (br. s. 10-NH): 10.42 (br. s. 1,1’-H)
6.93 (dd, J=8.6+2.1 Hz, 5-H): 7.16 (d, 2.1 Hz, 7H); 7.24-7.80 (m. 5’,6’,7’-H); 8.96 (d, 8.6 Hz, 4H): 9.15 (broadened d. 7 9 Hz, 4-H): 9.64 (br s,
10-NH): 11.65 (br. s. l.l’-NH)
(4)
h,,,=422
(log€ 3.34):
330.5 (4.29). 318 (sh,
4.09); 280 (3.70); 270
(3.66): 255 (sh, 3.77); 229
(4.14)
3420 br. s, 2960 s, 2880
m, 1740 w, 1710 s, 1635
(I)
(5)
h,,,=47I
(IogE 3.68);
362(3.51). 283 (sh, 3.83),
273 (3.82). 226 (4.44)
S
br. s
6.89 (dd, J=8.4+2.2 Hz, 5,5’-H); 7.13 (d, 2.2 Hz.
7,7’-H): 8-93 (d, 8.4 Hz. 4,4-H); 9.56 (br. s, 10NH); 11.92 (br. s, l,l‘-NH)
3420 br. s, 1760 w, 1710
ss, 1625 w, 1510 m. 735
7.0-7.40 (m). 9.82 (br. s, I.I’-NH); 11.22 (very
br. s, 10-NH)
s
92’ (C-3); 112.4 (CH): 116.1 (CH): 123*: 124.5’.
125.9 (CH); 133*, 143.2 (C-72): 153.2’ (C-2);
177.0 (C-9)
[a] 90-MHz: 6 values, TMS (int.). [b] The signals marked with an asterisk are broadened by coalescence; assignment of the signals of coupled spectra by selective decoupling and increment calculation
Arcyriarubin B has the structure and composition (i), in
agreement with all the spectroscopic data.
Like (2), arcyriaflavin C is composed of two identical
moieties. The absence of the 2,2‘ H-signals and the unusual
downfield position of the 4,4’H-signal at 6 = 8.93 are consistent only with structure (4).The structure is confirmed by the
transformation of (2) into (4), which already occurs on gentle
warming in conc. sulfuric acid. Arcyriaflavin B (3) has only
one OH group, and an additional downfield signal is consequently observed in the ’H-NMR spectrum at 6=9.15.
Especially interesting is the third red pigment,
CZoH,‘N303,which shows a reversible color-change to violet
on TLC plates over NH3 vapor. According to the IR spectrum it contains the maleimide system and has a symmetrical
structure. The absorption spectrum strongly resembles that
of the reference compound (6), which is readily accessible in
60% yield by condensation of indolylmagnesium iodide with
1 -methyl-3,4-dibromomaleimide
in benzene at 25 “C in the
presence of a small amount of hexamethylphosphoric triamidel’’. In the 400-MHz ‘H-NMR spectrum of the pigment,
three protons of the benzene ring are clearly recognizable
[6=7.18 (“t”, J = 8 Hz); 7.32 (br, “d”, 8 Hz); 7.38 (“d”, 8 Hz),
while the shape and position of the fourth depends very
strongly on the measuring conditions[6’. Since the indole
NH-protons give rise to one singlet at 6 = 9.82 and no signal
is observed for the 2,2’ H, the third oxygen atom can only
link the two indole rings; hence the pigment called by us
arcyroxepin A must have the formula (5).
C H?
H
H
(5)
H
H
(6)
The arcyriaflavins are structurally related to staurosporin,
an antibiotic and antihypertensive which has recently been
isolated from Streptomyces ~taurosporeu~~’~.
In the platelet
diffusion test, (i), (2) and (5) exhibit medium inhibiting action against Bacillus brevis and B. subtilid’].
Received: March 26. 1980 [ Z 464 IE]
German version: Angew. Chem. 92, 463 (1980)
460
0 Verlag Chemie. GmbH, 6940 Weinheim, 1980
CAS Registry numbers:
( I ) , 73697-62-8; (2). 73697-63-9; (3).73697-64-0: (4).73697-65-1; (51, 73697-66-2
~
~~
[ l ] Cf. K. Miigdefrau in E. Strasburgerr Lehrbuch der Botanik. 31st Edit. Gustav
Fischer, Stuttgart 1979, p. 596.
[2] Carotinoids in Lyrogala epidendronr S. Liaaen Jensen. Phytochemisiry 4,925
(1965).
131 Cf. 3-methylmaleimide: 6(CO)= 173.2, 6(C-3)= 128.2: M.-T. Chenon. R. J.
Pugmire, D. M. Grant. R. P. Panzica. L. 8.Townsend. J. Heterocycl. Chem.
10.427 (1973)
[4] Cf. e.g. M. Shamma, D M. Hindenfang: Carbon-I3 NMR Shift Assignments
of Amines and Alkaloids. Plenum Press, New York 1979.
[5] (6) m.p. 276-278°C: UV (CH,OH): h.,,,=465 (Iogc=3.90). 371 (3.74).
284 (sh, 4.10). 276 (4.14), 248 (sh, 4.23); IR (KBr): 3460 m. 3320 m, 1760 w,
1690 VS. 1615 W, 1535 S, 755 vS, 745 VS;‘H-NMR (CDKOCD,): 6=3.10 (s.
CH,); 6.64 (“t”, J = 8 Hz); 6.94 (“d”.8 Hz): 7.00 (“t”, 8 Hz); 7.42 (“d,8 Hz);
7.87 (d, 2.8 Hz), 10.80 (br. s): “C-NMR (CD,OD): 6 = 107 3 (C-3). 1 1 1.9 (C7). 120.2 (CH). 122.2 (CH), 122.5 (CH), 126 6 (C-3a). 128.3 (C-8). 129.5 (C2). 137.2 (C-7a). 173.6 (C-9).
161 We thank Dr. W. E Hull, Bruker, Karlsruhe, for recording the spectra.
[7] A. Furusaki, N. Hashiba, T. Matsumoto, A. Hirano. Y. In3aI. S. Omura, J .
Chem. SOC.Chem. Commun. 1978. 800.
[8] T. Anke. unpublished.
Sequence Analysis of Ergochrome-Biosynthesis by
Competitive Incorporation‘”]
By Burchard Franck, Gerhard Bringmann, and Georg
Flohrr’l
Information about alternative intermediates is of cardinal
importance for an understanding of natural product biosyntheses and for the development of biomimetic syntheses. By
means of competitive incorporation[’] we have been able to
detect alternative intermediates in the biosynthesis of mycotoxins of the ergochrome type[21,e. g. of secalonic acid D (5),
and to assign them to an informative sequence.
Ergochromes are formed by oxidative ring ~ p e n i n g [of~ . ~ ~
the anthraquinone emodin (i), a key building block in the
[*] Prof. Dr. B. Franck. Dr. G. Bringmann
Organisch-chemiscbes Institut der Universitat
Orleansring 23, D-4400 Miinster (Germany)
Dr G. Flohr
Unilever-Forschungslaboratorium
Behringstrasse 154, D-2000 Hamburg-Altona (Germany)
[“I Metabolites of Fungi. Part 30.-Part
Tetrahedron Lett. 1980, 1185.
0570-0833/80/0606-460$ 02.50/0
29: B. Franck. H . Barkhaus. M. Rolf.
Angew. Chem. I n t . Ed. Engl. I9 (1980) No. 6
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