N Me
Me
NH
Me
+
BF 4
BocNHNH 2
HN N
N OH
OH
MeO
MeO
I
1
5
2
3
4
1) EtSO 2Cl, Et 3N (2 eq) THF, 0 °C, 70%
2) n -BuLi (1 eq), THF, –78 °C;
MoO 5·HMPA-LDA in THF (1.1 eq), –78 °C; rt ; water, 45 °C, 81%
1) NaNO 2, aq AcOH, 10 °C 2) PPh 3, Et 2O
3) Cl 3CCHO, toluene, reflux
4) Oxone, K 2CO 3, H 2O-CHCl 3, 0 °C
Reagent A
1) A , CH 2Cl 22) TFA
宣毒发表汤
3) NIS (2.5 eq)
S
O
1) CH 2N 2 (gas), Et 2O, –78 °C, 87%2) , CH 2Cl 2, reflux, 63%3) TFA, CH 2Cl 2, 70%
PhOC COPh S
Ph
HO COPh
Cl Cl O O
2 eq PhP(SiMe 3)2CH 3CN, –15 °C
MeOH reflux, 24 h
OMe OMe O O
S
N CN H 3C
CO 2Et O
N 2
[Rh(OAc)2]270 °C, 1 h
S
CH 3
CO 2Et
NC
O
N O
140 °C, 1 hr
+
O
C 26H 38O 2P 2Si 2
O OH
-
P(OEt)3 (1 eq.)40 to 100 °C, 1 hr A 99%
LDA, THF, –78 to 0 °C;A , Pd(PPh 3)4, rt, 3 hr;
NaOH, EtOH-H 2O reflux, 24 hr
H Si H
SiMe 2Ph
PhS
H HO
H
SiMe 2Ph
1) NaIO 4
2) heat, PhH 3) H 2O 2, KF KHCO 3
Cl
O Cl
O
O
H 3N
CO 2
A
(OC)5Cr
OBn
Me
MeO 2C
CHO
BnO Me O
CHO N N Ph Ph
Ph
Ph
Br
N
MeO Br 1
5
2
3
4
79%
枣核
续编故事
1) LAH
2) HCO 2Et
h νA 76%
HCl (g)MeOH;I 2
acetone/H 2O
(E :Z =59:41)
1) Ca(OCl)2, CO 2, H 2O CH 2Cl 2, 65%
2) cat. Pd(OAc)2, Ph 3P, AcONa 150 °C, 66%
3) Lawesson's reagent
PhMgBr (2.2 eq)
THF –42 °C to rt
OTMS
北大语料库t -BuO 2C
SPh
PPh 3BF 4
O
O
O
NH 2
OH Ph
N O
O Ph
R Ts
NC Se
Ts
H NC OH
1
5
3
4
1) N 2CHCO 2Et, CuSO 4, PhH, 65%
2) , KF, 18-crown-6, MeCN, 82 °C, 95%3) NaOH / H 2O, MeOH, THF, 60 °C
4) ClCO 2Et, Et 3N, THF; NaBH 4, THF / H 2O 5) TFA, CHCl 3, 43% (3 steps)
aq. glutaradehyde (2.5eq) pH3.5 , TolSO 2Na ; ZnBr 2
R : TolSO 2
1) CH 2N 2 (ex.), CH 2Cl 22) mCPBA, CH 2Cl 2, – 10 °C
Cl
O
OMEM
OH t -BuOOH cat. VO(acac)2
CH 2Cl 20 °C
OHC
MEMO
O
H
H
OH
56% (2 steps)
O N
Ph
OCH 2OCH 3
n -Bu
OCO i -Bu
CH 3
1) BF 3•OEt 2 (3 eq), PhSH (5 eq) CH 2Cl 2, rt, 1.5 h, 57%2) W-lump, O 2, rose bengal CH 2Cl 2, 3h, 35%
O
O
H 3C
n -Bu i -BuCOO Ph