New trihydroxylated tetrahydroanthraquinones from fungi of the genus Dermocybe

Tetrahedron Printed in

Letters,Vol.30,No.Sl,pp Great Britain

NEW TRIHYDROXYLATBD

Department

of Organic

J. Burns, Melvyn

Chemistry,

University

+

.OO

FROM FUNGI OF THE GENUS DERMOCYBE~

T~TBAHYDR~ANTHRAQUIN~NBS

Christopher

004o-4039/89 $3.00 Perqamon Press plc

7269-7272,1989

Gill*

and Albert0

of Melbourne,

Gimenez

Parkville,

Vie.

3052, Australia.

Summary - The pigments 6, 7 and 8, the first trihydroxylated tetrahydroanthraquinones from Basidiomycetes, have been isolated from an Australian toadstool belonging to Dermocybe; the absolute stereochemistry of each pigment is established by synthesis.

There

is continuing

quinones

such as bostrycin

pathogenic

microorganisms,

biologically

Dermocybe

toadstool

here

trihydroxylated

of the pigments with

in a related

by spectroscopy

occurring

We earlier

tricyclic

toadstool

class.5

the only

to be found to date in Basidiomycetes, analogues

of anthracyclinones

We

structures

represent

of the rhodomycinone-

0

HO

HO

Me0

0

HO

OH

OH

0

0

Meo*;H Ma’= OH

0

OH

OH 6 Fi'=OH,Ra=H 7 R'-H,R2=0H

of the fresh

fungus9

three diastereoisomeric m.p.

4

bH

5

x 10-3% fr,wt.),

R

2 R-OH 3 R=H

1

derivative

structural

to which

These pigments,

in the

group. 8

0

separated

notable

of the feudomycinone

Me0

Extraction

the occurrence

of three new quinones

and synthesis.

of

of this small class of

reported

4 and 5, which bear

anthracyclinones

of tetrahydroanthra-

A (2)3 and B (3),4 constituents

of new members516

matters.

tetrahydroanthraquinones

the first naturally citromycinone

colouring

splendida

6, 7 and 8 are assigned

and stereochemistry

(l)* and the altersolanols

similarities

the occurrence

in the synthesis

and in the discovery

natural

potent'

and stereochemical report

interest

72-75OC,

with ethanol

yellow

pigments,

followed

of 5-hydroxy-1,4_naphthoquinone

430 run)16 and from the appearance

by extensive

7269

spectrum

chromatography

The predominant

was

from the electronic

in the k-n.m.r.

OH

6

CLoH1607.

[a]D -323O (c 0.35, CHC13)

0

identified spectrum

of methoxyl

isomer

6 (4.4

as a (XgkzH 229, 269, and phenolic

1270

hydroxyl

singlets

coupled region

aromatic

at 6 3.92 and 12.08, proton

of the n.m.r.

couplings

observed

stereochemistry Hz) between (possible

resonances

spectrum

of 6 are summarised

are entirely

shown.11

respectively,

consistent

Of particular

l-H,, and 2-H,,

with

a pair of meta-

with

Signals

in the aliphatic

in Fig. la.

The chemical

the structure,

conformation,

note are (i) trans-diaxial

(ii) W coupling

only if 3-OH is strongly

and (iii) the lack of W coupling

together

at 6 6.65 and 7.19.

hydrogen

between

(J 1.8 Hz) between bonded

coupling Z-H,

shifts

and

and relative (J 9.2

and 3-OH

to a cis-disposed

2-Heq and the methine

proton

hydroxyl

proton

at C-4),

at C-4.

6 1.Bg, ddd, 13.9.9.2 8 1.8 Hz 6 4.50. dd.

3.3.4.4 a 2.9 Hz I 8 5.15. dddd.

\

6 4.42.d. 68

92,6.2,2.6&1,8H7

0-l-i

Hz

S 3.23, d. 2.2 Hz

Figure

The absolute 1) beginning

lo-n.m.r. data (CDCl3) for aliphatic protons, (a) in 6, and (b) in 7.

1.

configuration

from the natural

The synthetic

substance

(cf. Fig. la)

indistinguishable

rotation

of 6 was established product

10, m.p.

of 10 {[a]D +330°

9 of known

72-76OC,

by synthesis

structure

of its antipode

and absolute

is chromatographically

from the natural

(c 0.4, CHC13))

the lR, 3R, 45 stereochemistry

establishes

and hydroxylic

product

6.

with the value for the natural

and spectroscopically

Comparison

cited

10 (Scheme

stereochemistry.l

above

of the specific for 6 then

product.

0

OH

a,b.c.d 9% 10

9

Scheme

Reagents: a. (CF3C0)2O, OOC, 15 min; b. Erg, hv, 45OC, 3O*C, lh; d. 0.5M NaOH, !I%, 30 min.

1.

A second differs observed hydroxyls

isomer

from

7 (2.7 x 10m3%

6 in the aliphatic

couplings

stereochemistry

proton

(Fig. lb) define

in 7 occupy

fr.wt.),

m.p.

region

that half

74-80°C,

[a]365 +350°

of the n.m.r.

shown

by synthesis

from the natural

DMSO,

(c 0.6, CHC13)

spectrum,

chair conformation

the same mean face of the tetrahydroaromatic

of 7 was established

2h; c. CF3C02Ag,

In this case the in which.the

ring. product

three

The absolute 5 of known

7271

absolute

configuration.

analogous

to those

epimeric

Thus, benzylic

at C-4, which were

[a]365 +520° product

1

depicted

7.

(c 0.4, CHC13) Furthermore,

The second

by chromatography.

and synthetic

m.p.

?5-82OC,

(cf. Fig. lb) from the natural

indistinguishable

order

One of these,

Cl6Hl607,

materials

of magnitude12

possess

a specific

thus establishing

rotation

of

1.9, 3R,

for the fungal metabolite.

tetrahydroanthraquinone

identical

obtained

from the toadstool

spectroscopic

8 (1.0 x 10m3%

chiroptical

of reactions

separated proved

the natural

exhibits

product

of 5 via a sequence

1 gave a pair of tetrahydroanthraquinones,

the same sign and of a similar 45 stereochemistry

hydroxylation

in Scheme

properties

45 stereochemistry

11, m.p.

properties

extractives.

fr. wt.), m.p. {[a]D CHC13

93-9E°C,

with That

obtained

the third,

11 represents

93-9E°C,

was evident

8 -152O, 11 +157O)

upon hydroxylation

and least abundant, the antipode

of the natural

from comparison

which

of 5

pigment

of the

lR, 35,

establishes

for 8.

0

OH

11

In view developing isolation prove

of the importance taxonomy

of these more highly

significant.

compounds

of anthraquinone

of Dermocybe

Tests

described

hydroxylated

are currently

herein

classification

and the results

and for lodging

Conservation,

Forests

jurisdiction.

Financial

and Lands support

(to M.G.),

the Commonwealth

University

of Melbourne

analogues

Royal

for permission is acknowledged

Part 13 in the series

2.

T. R. Kelly,

'Pigments

Botanic

specimens, to collect

of Fungi'.

to the the

activity

of the

in a full paper.

Garden,

Edinburgh

and the Department fungi

in National

from the Australian

award

References

1.

the biological

(for a postgraduate

(for a postgraduate

pigments

hemisphereI

6, 7 and 8 of 5 and 9 will no doubt

to assay

will be reported

herbarium

of Australia

in the southern

underway

Acknowledgements - We thank Dr R. Watling, with

and pre-anthraquinone

and its allies

award

for help of Parks under

Research

Grants

to C.J.B.)

its

Scheme

and the

to A.G.).

and Notes

Part 12:

J. Chem. Sot., Perkin

Transactions 1, submitted.

Whittle,

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17.

Kelly

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Lett.,

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All assignments

12

The specific at shorter

13

are supported

rotation

wavelengths

accurate

M. Gill and W. Steglich,

(Received

in

by proton

decoupling

of 7 at 589 nm (sodium measurement

Fortschr.

UK 17 October

and D20 exchange

D line)

is close

is impaired

Chem. Org. Naturst.,

1989)

experiments.

to zero.

by absorption 1987,

51, 125.

Unfortunately, of radiation.