Title Synthesis of 14α-methylcholesterol

Sub Title
Author 高橋, 恭子(Takahashi, Kyoko)
宇佐美, 恵子(Usami, Keiko)
高橋, 環美(Takahashi, Tamami)
岡田, 智子(Okada, Tomoko)
森崎, 益雄(Morisaki, Masuo)
Publisher 共立薬科大学
Publication year 1987
Jtitle 共立薬科大学研究年報 (The annual report of the Kyoritsu College of
Pharmacy). No.32 (1987. ) ,p.74- 75
JaLC DOI
Abstract
Notes 抄録
Genre Technical Report
URL https://koara.lib.keio.ac.jp/xoonips/modules/xoonips/detail.php?koara_id=AN00062898-0000003
2-0074
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 N
o.32 (
198
7)

Synthesis of 14aMethylcholesterol*
圃

KyokoTAKAHASHI,KeikoUS
AMI
,TamamiTAKAHASHI,
TomokoOKADAandMasuoMoRISAKI

高橋恭子，宇佐美恵子，高橋環美，岡田智子，森崎益雄

L
ano
ste
rol(
1), throughac
onv
ent
ion
alf
ours
tepsequence (
cat
aly
tich
ydr
oge
nat
ion
,
a
cety
latio
n, chromic acido
xidati
on,r e
ducti
on with z
inc-a
cetica c
id) was c o
nvertedt o
the7,1
1-diket
on e(2)in59% yiel
d. Weavoidedt hehazardousWolff-Kishnerr e
ductio
n
t
oremovet he7 ,11oxygenf
『 unc
tionof2andi ns
tead
,d eac
etoxylat
ionoft he7 ,1
1-diac
etat
e
()wasp
3 er
form e
d. Thust h
el at
ter
,d er
ivedfrom2 bys ucces
sivesaponif
icati
on,t e
tra
-
hydropyranyl e
the
rfo
rma
tio
n, LiAlH4 r
edu
cti
on and a
cet
yla
tio
n witha
cet
ica
nhy
dri
de-

a b

HO AcO THPO

2 3

e d
b
・ ・ 圃 ・ 圃 圃 圃 圃 園 圃 園．
．

HO
(
j ,
r

g h
−・輔幽園田園圃圃園開・・・．

HO
7 8 9
(
a)i
,H2/Pd-C/Ac0Et;ii
,Ac20/pyr
.;iii
,CrOa/AcOH;iv,Zn/AcOH.
(
b)i
,KOH/MeOH;i i
,d i
hydropy
ran/Am
berly
st1 5/CH2
Ch;iii
,L iA
IH./THF;i v
)Ac20/DMAP/pyr.
(
c)i
,Na/HMPA/tert-BuOH; i
i
,HCI/MeOH-CH2Ch・
(
b),
iPCl5
/n-hexa
ne;ii,Oa/CH2ChandthenZn/AcOH;i i
i
,KOH/MeOH.
(
e)i
,CFaCOOH/CH2Cl2;ii
,Jonesoxi
d.;ii
i,Ac20/HCI
O.・（f)CHaMgI/EhO-CsHs.(
g)NaOH/MeOH.
(
h)i
,CH2=C(OAc)Me ／ρTsOH;i i
,NaBH./MeOH-THF.

事本報告は C
hem
.Pharm.B
ull
.,3
5,3467-3469 (
198
7）に発表．

-74-
 N
o.32 (
198
7)

pyrid
inei nt hep resenceof4 -dimeth
ylaminopy
ridine, was subj
ectedt or eacti
onw i
th
sodiuminh exame
thylphosphorictriam
ide/
tert-b
utan
ol.S u b
sequentacidt r
eatmenta f
forde
d
lano
stanol(4)in61%o ver
allyieldf rom2
.T ransfor
mationof4i n
tot hee no
ll acton
e( 6
)
viatheA引 or- keto
ne( 5
),wase 百ectedesse
ntial
lybyt hereporte
dmethodi n18%y ield
.
Grignardreact
ionof6withm e
th ylmagnesiumi odid
egavet hemasked1 ,5-diket
one(7)in
75%y ield
. Thel at
terhadn eithercarbony
la bsorpt
ion( in
frare
dandc arbon-1
3n uclear
magneticr e
sonance
)n orano lefin
icbond( 1H-and13C-NMR),andwasmuchmorep olar
thant hestart
inge no
ll acto
ne( 6)ont hi
nl ayerchromatogra
phy. O therNMRs ign
alsa s
wellast hemasss pectra
lp eaka tm /z416 (M-18)s trong
lys uggeste
dt h
ed ihe
miaceta
l
stru
cture(7)
,a lthoughit
ss t
ereochemis
tryrem a
inedu nde
termined. Alkalinet reat
mento f
7gavet he3-oxo-
4-one(8).E no
la cety
lati
ono f8w i
thi sopr
openy
la ce
tate／ρ−to
luenes
ulfoni
c
ac
id,fo l
lowedbyr educt
ionw ithNa 四Lf urn
ished14αm
嶋 ethylc
holeste
rol( 9,42%)
,t ogether
withits3-epim
er( 4%). Thes p
ectrosc
opicdataof9u ne
quivocal
lyestablis
hedt hestru
ctur
e.

-76-