O O

S
PPTS = O
N
H

A H
OAlH2
OMe OMe H
LiAlH4 H Al H
H
OH O

H H
H Al H
OAlH2
O

O
O
H H OBz
OTIPS OTIPS H HO
OH H H
O H
PMBO PMBO O OH
HO H H
CN
H
C F H M H
convex (lõm)

O DIBAL concave (loi^`) O

O O
O
N
O O H
H O
H H

H
OH
TESO
O P

PPh3
I I I PPh3 (tac nhan halogen hoa: CCl4, CBr4, I2)

I PPh3 I
PPh3
R OH R O R I
- H+
 C -> D: Regitz diazo transfer

1: 1. DIBAL; 2. NaBH4
2: 1. OsO4/NMO 2. TESCl
3: 1. DMP; 2. TBAF

PhSH: PMB-byproduct scavenger

 O
O HO O 4-pyrrolidinopyridin (1 eq) 1. DIBAL-H, -78 to 0 oC
2 (C10H14O2)
TsCl (1.5 eq), K2CO3 (3 eq) 2. i. TsCl, LiBr, pyridin, 23 to 60 oC
DIPEA (4 eq), DCM, 2 h ii. (EtCO)2O, Et3N, DMAP, rt

(R)-carvone 1

O
HO O OX conjugate reduction O

O
O 1. Li/NH3 OTMS NaIO4 HO O

2. TMSCl OsO4

O SET O O NH O SET O
3

O
OH
O 1. Li/NH3 O NaIO4 HO O

2. Davis oxaziridin
O O Cl O O
O OH O O S O OTs N N
B O

N N
O O
O
O N B O N OO
O
NR2
H

A: i. NaH; ii. MeI

B: Li

C: Grubbs

D: CH2I2, Cu/Zn (or: Charette)

 OTBS i
Pr 1. LDA, Tf2O
CO2Me 1. i. DIBAL; ii. DMP

AlCl3, dr = 2:1 SnBu3 MgCl

TBSO 2. 2.
Pd(PPh 3)4, LiCl dr = 6:1

i
Pr
t o TBAF 1. DMP KHMDS, 0 C o
O
F G
2. DIBAL, MsCl, dr = 2,5:1

OH OH
HO MsO
MeO2C MeO2C i i i
OTBS OTBS Pr Pr Pr
OTBS
i i
Pr i OH
Pr Pr OTBS OH

O
A Stille coupling [C] [D] E F
B

MsO MsO
i i
i
Pr N Pr Pr
O TMS TMS O O
H

Cl Cl

O O
Br

O O O O OH O
OH
H

I K L M N

TBHP OH
VO(acac)2 V Ot
L O Bu
L

R
OH RtBuO L R
V Ot V L
L O Bu O O OVL2OtBu
OH L O

O O
O

R R

O OVL2OtBu O O VL2OtBu TBHP O

O O O
OH
 O O i
Pr i
OH IBX Pr
O
OH O
O O
O CF3 O OH
O
[P] Q
O

i i
Pr Pr
O O
CO2Me

OH OH
R S

i i
i
Pr Pr Pr
O O O O OH PMe3 OH
O OH OH - + OH
+ H
OH H OH OH

i
i Pr O
Pr
O
O O O
O OH OH

OH OH H

i i i
i
Pr Pr Pr Pr
SmI2 OSmI2 OSmI2 SmI2 OSmI2
O

O O O OSmI2

Cl

Cl H- MeO H
SO2Cl2 K-selectride O
O
Na2CO3 Cl
O O O
Cl

O O H
S
Cl Cl Cl
Cl
 OBn OBn OAc
BnO CHO 1. BnO CHO 2. MgBr2·Et2O BnO CHO 4. MeNO2, KF, 18-crown-6

3. NO2 5. Ac2O, NaOAc

NO2

1. HNO3
3. Ac2O, Et3N Br LA
6. H2, Pd/C Ph O O OLA O OH O
9. SEMCl, Et3N
13. H2, Pd/C BnO BnO work-up BnO
H H
OBn NO2 NO2 NO2
BnO CHO

NO2

BnO
BnO O Ag+
BnO
OH Br

NaH
H2O HO-
O
O O NMe2 O
H NMe2 OH
R CF3 R O H R O
 O

Li CuRLi A

I Li TBSO

O O Cl Cl O Cl Cl
O O O AcO
CCl3

TBSO TBSO TBSO TBSO

2 3 4 5

O Cl Cl O Cl Cl O Cl Cl
AcO AcO AcO

OAc
TBSO TBSO O TBSO O
OH
Chemical Formula: C30H48Cl2O7Si
6 8
7 (C30H48Cl2O7Si)
O
Cl Li AcO Cl
AcO O Cl AcO O Cl

O TBSO O
TBSO O TBSO

HO
HO

TBSO O

OH Charetta cyclopropanation OH I2, PPh3, imidazole I

OH O
1. TBSCl, Et3N PDC, TBHP

2. Grubbs
TBSO TBSO