N Boc N Boc N Boc

H H+ - H+
N N N
H H O H O

NH N Boc
N
H+ Boc2O
N N
N H O
H O H O

N Boc

N
O O

NH2 NH NBoc NBoc

OH
N N N N
H H HO H HO H O

NH2 NH NBoc
Boc2O NBoc
O
N TFA N N
H H O N
H O H O
4:1
60%

NBoc i- LHMDS (2 eq.)

ii- PIDA (2 eq.)
N
H O I(OAc)2
 O
c: O
1) NaBH3CN, AcOH, MeOH O
O
NaBH(OAc)3, DCM HN
2) TFA N
N
N H
H
3''
3' g
O
f
i- LHMDS (2 eq.) O
O
O BocN ii- PIDA (2 eq.)
NH2 a O b c
BocN HN
N N N
H TFA H N H
1 2 3 4
d d
O O
OH H OH
MgBr
HN e
N BocN BocN
N N
H N N
5 Aborisidine 4' 5'

1) LDA O
CHO 2) Thêm 3
3) Thêm Ti(Oi-Pr)4 O
a) < 2 steps b) < 3 steps Thêm LDA O H
O O
O
O
1 2 4

O O
O
O
3
O LDA
OH O O
O O c) < 2 steps
3 O
O
5
O O OH
O
O
O O OH
H
O O
O
O O
4 (-)-Jiadifenolide
O H 2C

Thêm Ti(Oi-Pr)4 Làm ben anion O

Thêm LDA tao dianion Ti
O O
 O OH O
amino carbonyl
O

R' N N
N R" O

O OH OH
O

R'
N R" N N N

O O
O XMg
N R" OEt
NH2

O OH OH
O
R' R' R'
N R" N R"
N N
R"

O
O R' OH
M
R' HO R'
HN HN
N
R" R"
R"

O R'

O
X R'
NH2
R" N
R"

O O O OH
Ph
Ph N
N
N
a H
b c O
 DPPA
R OH R N3
O
Ph P Ph
N3 (DIAD, PPh3)

CH3 CH3
HN3, DEAD
PPh3 HOSO2Cl
R OH R N3

SO2Cl

Cs2CO3

OBn
I

1) NaH, epoxyde
2) HI

O
BnOH
DPPA
DIAD, PPh3
 M

NfF O
S
C4H9 F
O
O
R R
BTPP = NtBu
P
N N
N

Pd(OAc)2 K2Cr2O7
CuCl2, O2 H 2O
Wacker O O
O H OH
O

hetero-Pauson Khand
 Co2(CO)8 Co2(CO)8
C O O C O O
CO (p, t) CO (p, t) O
O

OTf OMe
Pd0 O
C O CO (p, t)
MeOH
Ko phai Pauson Khand

Br
NaNH2
CNa

O OH

Br Bu3Sn-SnBu3
O O
Bu3SnH