(+)-Aurilol (TKGP-090704) Y.

Morimoto1)

Me
Me H
O
OH
Br
Me
O O O
Me Me H H Me H OH
MeOH Me

Activity Cytotoxic（細胞毒性）
(A) stereospecific THF ring formation, (B) regioselective 5-exo-tet cyclization
Key Reactions (C) regioselective Shi asymmetric epoxidation, (D) regioselective 6-endo-tet
cyclization, (E) 7-endo-trig bromoetherification

AD-mix-β OH 1) ? ?
? ? O ? O
OH O O
OAc t-BuOH-H2O 2) K2CO3
OAc MeOH OH SPh
1

###

?
1) mCPBA OHC 1)? ?
OAc 2) ? OAc 2) K2CO3 OH SPh
THF-H2O MeOH B-95
2
###

1) LDA HO TBHP
TMSCl 1) LiAlH4 ?
?
CO2Me 2) TiCl 2) TBSCl ?
4 C-67
imidazole OTBS MS 4A

1) SEMCl TBHP NaOH

HO SEMO SEMO
O ? O ? O dioxane

2) TBAF ? O reflux
OTBS OH MS 4A OH
(A)

1) MsCl O
pyridine OSEM 1 O ?
? OSEM
2) ? O BuLi i-PrOH
HO H H O
? ? O THF
HO H H OH
SPh
 O
O O

O O
O O O
O O 1) ?
OSEM OSEM
? O 2) TBAF
O DMM-MeCN-H2O O
HO H H OH buffer (pH 10.5) HO H H OH (B)
B-45, 102

1) MsCl
O pyridine O 2
O O
HO O O 2) ? O O BuLi
HO H H H OH ? O H H H OH ?

O
O O

C-33 O O
O O
PhS ? O
O
O i-PrOH ?
O O THF O DMM-MeCN-H2O
HO H H H OH O H
HO H H OH buffer (pH 10.5)

(C)

O ?
O TIPSO
? O
O O
MeNO2 O O O
O O H H H OH
HO H H H OH
(D)

?
HO
1) TBAF O MS 4A
O
2) ? O O O (CF3)2CHOH
Me2C=CHMe H H H OH
C-97
(E)

H H
O O
O aq AcOH OH
Br O Br
O O O O O O
H H H OH H H H OH OH

(+)-Aurilol

Reference:
1) Y. Morimoto, Y. Nishikawa, M. Takaishi, J. Am. Chem. Soc., 127, 5806 (2005)