0181
J[ R[ HANSON et al[
IR ymax cm−0 2364\ 0614\ 0601^ 0H NMR dH 0[96 and cꢁ11[518"2# A\ aꢁbꢁgꢁ89> Vꢁ0565[8 "3# A2 Zꢁ3\
0[97 "each 2H\s\ H!07 and H!08#[ Elution with 34)
EtOAc!petrol gave 2b\ 03a!dihydroxy!4a!androstan!
05!one "02# "54 mg# which crystallized from EtOAc!
petrol as needles\ mp 125> "decomp[# "Found] C\ 63[4^
H\8[6[C08H29O2 requires C\63[4^ H\8[8)#^ IR
ymax cm−0 2310\ 0626^ 0H NMR dH 9[76 "2H\s\ H!07#\
0[94 "2H\s\ H!08#\ 2[50 "0H\tt\ Jꢁ4 and 00 Hz\ H!2#[
Elution with 49) EtOAc!petrol gave 6a\ 03a!dihy!
droxy!4a!androstane!2\ 05!dione "03# "35 mg# which
crystallized from EtOAc!petrol as needles\ mp 127Ð
128> "Found] C\ 60[3^ H\ 7[8[ C08H17O3 requires
C\60[1^ H\7[7)#^ IR ymax cm−0 2300\ 2239\ 0621\ 0601^
0H NMR dH 0[94 and 0[95 "each 2H\s\ H!07 and
H!08#\ 3[04 "0H\br[s[\ H!6#\ 3[58 "0H\s\ OH#[ Further
elution with 49) EtOAc!petrol gave 5b!hydroxy!4a!
androstane!2\ 05!dione "04# "068 mg# which crys!
tallized from EtOAc!petrol as needles\ mp 108>
"Found] C\69[8^ H\8[1[ C08H17O3 requires C\60[1^
H\7[7)#^ IR ymax cm−0 2340\ 0613\ 0696^ 0H NMR dH
9[84 "2H\s\ H!07#\ 0[14 "2H\s\ H!08#\ 2[79 "0H\br[s\ H!
5#[
D
calc[ ꢁ0[16 g[cm−2\ F"999# 585\ monochromated
Mo!Ka radiation gꢁ9[60962 A\ uꢁ9[98 mm−0
Data were collected using
a
crystal
ca[9[29×9[04×9[04 mm on an EnrafÐNonius CAD 3
di}ractometer[ A total of 2256 re~ections were col!
lected with 1³u³14> for 9³h³6\ 9³k³03\
−15³15 and 1088 re~ections with 0×19"I# were used
in the re_nement[ There was no crystal decay[
The structure was solved by direct methods using
SHELXS!75 and non!hydrogen atoms were re_ned
anisotropically by full matrix least squares on all F1
using SHELXS!82[ The hydrogen atoms were
included in riding mode with Uiso"H# equal to
0[1Ueq"C# or 0[4Ueq"C# for methyl groups[ Hydroxyl
groups were _xed at idealised geometry but with the
torsion angle de_ning the H atom positions re_ned
and Uiso "H# equal to 0[4Ueq"O#[ The _nal R indices
ðI×19"I#Ł were R0ꢁ9[951\ WR1ꢁ9[044 and R indices
"all data# R0ꢁ9[975\ WR1ꢁ9[062[ The crys!
tallographic data have been deposited with the Cam!
bridge Crystallographic Data Centre[
Further elution with 59) EtOAc!petrol gave 2b\
5b!dihydroxy!4a!androstan!05!one "05# "098 mg#
which crystallized from EtOAc!petrol as needles\ mp
073Ð074>\ "Found] C\ 63[1^ H\ 8[7[ C08H29O2 requires
REFERENCES
0
C\63[4^ H\8[8)#^ IR ymax cm−0 2303\ 0627^ H NMR
0[ Browne\ J[ W[\ Denny\ W[ A[\ Jones\ E[ R[ H[\
Meakins\ G[ D[\ Morisawa\ Y[\ Pendlebury\ A[
and Pragnell\ J[\ J[ Chem[ Soc[\ Perkin Trans\
0862\ 0382[
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Pragnell\ J[\ J[ Chem[ Soc[\ Perkin Transl[\ 0862\
0\ 0499[
2[ Bell\ A[ M[\ Browne\ J[ W[\ Denny\ W[ A[\ Jones\
E[ R[ H[\ Kasal\ A[ and Meakins\ G[ D[\ J[ Chem[
Soc[\ Perkin Transl\ 0861\ 1829[
3[ Farooq\ A[\ Hanson\ J[ R[ and Iqbal\ Z[\ Phyto!
chemistry\ 0883\ 26\ 612[
4[ Hanson\ J[ R[\ Nasir\ H[ and Parvez\ A[\ Phyto!
chemistry\ 0885\ 31\ 300[
5[ Bridgeman\ J[ E[\ Butchers\ C[ E[\ Jones\ Sir
Ewart R[ H[\ Kasal\ A[\ Meakins\ G[ D[ and
Woodgate\ P[ D[ "0869# J[ Chem[ Soc[\ "C#\ p[
133[
6[ Ghilezan\ I[\ Jones\ E[ R[ H[\ Meakins\ G[ D[ and
Miners\ J[ O[\ J[ Chem[ Soc[\ Perkin Transl\ 0865\
0249[
7[ Barton\ D[ H[ R[\ O|Brien\ R[ E[ and Sternhell\
S[ "0851# J[ Chem[ Soc[\ p[ 369[
dH 9[80 "2H\s\ H!07#\ 0[06 "2H\s\ H!08#\ 2[57 "0H\tt\
Jꢁ4[1 and 09[6 Hz\ H!2#\ 2[73 "0H\d\ Jꢁ1 Hz\ H!5#[
"b# Under similar fermentation conditions 05a\ 06a!
epoxy!4a!androstane!2b!ol "00# "799 mg# gave\ on
chromatography on silica in 19) EtOAc!petrol the
starting material "369 mg#[ Further elution with 59)
EtOAc!petrol gave 05a\ 06a!epoxy!4a!androstane!2b\
5b!diol "06# "014 mg# as a gum\ "Found] M¦ 295[107
C08H29O2 requires 295[108#^ IR ymax cm−0 2368^ 0H
NMR dH 9[65 "2H\s\ H!07#\ 0[03"2H\s\ 08!H#\ 2[00
"0H\d\ Jꢁ2 Hz\ H!06#\ 2[25 "0H\m\H!05#\ 2[54 "0H\tt\
Jꢁ4 and 00 Hz\ H!2#\ 2[79 "0H\d\ Jꢁ1 Hz\ H!5#[
"c# Under similar fermentation conditions 2b\ 05b!
dihydroxy!4a!androstane "09# "0 g# gave\ on chro!
matography on silica in 39) EtOAc!petrol\ the star!
ting material "01 mg#[ Elution with 49) EtOAc!petrol
gave 00a\ 05b!dihydroxy!4a!androstane!2!one "07#
"36 mg# which crystallized from EtOAc!petrol as
cubes\ mp 193> "lit[ð0Ł\ 195Ð196>#^ IR ymax cm−0 2237\
0
0604^ H NMR "pyridine!d4# dH 0[05 "2H\s\ H!07#\
0[10 "2H\s\ H!08#\ 3[19 "0H\dt\ Jꢁ3[7 and 09 Hz\ H!
00#\ 3[50 "0H\dd\ Jꢁ4[5 and 7 Hz\ H!05#[ Elution with
59) EtOAc!petrol gave 2b\ 00a\ 05b!trihydroxy!4a!
androstane "08# "109 mg# which crystallized from
EtOAc!petrol as cubes\ mp 134Ð138> "lit[ð0Ł\ 149Ð
8[ Cookson\ R[ C[ and Coxon\ J[ M[ "0860# J[ Chem[
Soc[\ "C#\ p[ 0356[
0
140>#^ IR ymax cm−0 2273\ 2260^ H NMR "pyridine!
d4# dH 0[98\ "2H\s\ H!07#\ 0[19 "2H\s\ H!08#\ 2[89
"0H\tt\ Jꢁ4 and 09 Hz\ H!2#\ 3[12 "0H\dt\ Jꢁ3[7 and
09 Hz\ H!00#\ 3[46 "0H\dd\ Jꢁ4[4 and 7 Hz\ H!05#[
09[ Hanson\ J[ R[ and Nasir\ H[\ Phytochemistry\
0882\ 22\ 720[
00[ Ohlo}\ G[\ Maurer\ B[\ Winter\ B[ and Giersch\
W[\ Helv[ Chim[ Acta\ 0872\ 55\ 081[
01[ St[ Andre\ A[ F[\ Macphillamy\ H[ B[\ Nelson\ J[
A[\ Shabica\ A[ C[ and Scholz\ C[ R[\ J[ Am[
Chem[ Soc[\ 0841\ 63\ 4495[
Crystallo`raphic Structure Determination of "03#[
C08H17O3\ M!219[3\ orthorhombic\ space group
P101010 "No[08#\ aꢁ5[1689"09#\ bꢁ00[791"1#\