yield: 11-25%; ee: 4-85%
O
H
HO
N
H
N
HO
N
OMe
N
16,35%ee
O H
N
N Ts
O
+
Ar H
N
OH
15 (10 mol%)
TsHN O Ar
N Ts +
Ar H
O
15 (10 mol%)
R
74-99%ee TsHN O
Ar
R=H,OMe,OPh
67-89%ee
N P(O)Ph2 +
OH N
14 OMe 17-45%ee
Hatakeyama, S. * J. Am. Chem. Soc. 1999, 121, 10219-10220
HO N
RCO CF3 15 (10 mol%) OH O CF3
+ OO
O CF3 DMF, -55 oC R
O CF3 R
O
yield: 31-58%; ee: 91-99%
CF3
CF3
O OH Ar
60-94%ee 55-84%yield
S
CF3
NN HH
N
CF3
25 83%yield, 71%ee
S
CF3
NN HH
N
CF3
27 56%yield, 73%ee
CF3 S
NN NHH
CF3
26 21%yield, 39%ee
S
NN
Cl
HH
N
28 18%yield, ee ND
CHO
N OH
15 CH2Cl2, -20 oC
CHO HO R
O
R1
N R2 R3
70-96%yield 90-99%ee
Yixin Lu * Org. Lett. 2011, 13, 82-85
O H
N
N
O
OH COOBn
R1
O+ N R2
HO N
HO N
HO N
N
O
N
N
H NBoc
OH
N
S
CF3
N H
N H
37 Bn -30oC, 86%ee
15 -30oC, 77%ee
39 Rt,30%ee
CF3
Jian Zhou * J. Am. Chem. Soc. 2010, 132, 15176-15178
O R
O+
R1
N R2 R3
HO N
CF3
CF3
S
NN NHH
CF3
30
80%ee
S NN NHH 31
61%ee
OMe N
H
N HN
N
H S
31
65%ee
CF3
CF3 N
N H N HN H
S 33
80%ee
CF3 CF3
Jieping Zhu * J. Am. Chem. Soc. 2008, 130, 12596-12597
O NS
OH N OH
N
N
OH
OMe
5%yield, 24%ee 21
OH N OH
O OH N
OH
22
23
24
22-24, no reaction
Wei wang * Org. Lett. 2005, 7, 4293-4296
O O
+ Ar H
S NN HH N
25, 10 mol%
CH3CN, 0 oC
OH O R1 * Ph3P+
IV
Ph3P+
OII
R1CHO
O- O
R1
Ph3P+ III
主要内容
手性底物控制不对称反应 手性烯 手性亲电试剂
催化不对称反应 单手性催化剂 共催化
手性活化烯
CO2R＋* RCHO DABCO
OH R * CO2R*
DABCO
=
N N
yield: 15-95%, de: 2-100%
Ar H
O CF3 O CF3
15 (10 mol%)
TsHN O Ar
R=H,OMe,OPh
67-72%ee
Sasai, H. * J. Am. Chem. Soc. 2005, 127, 3680-3681
O R1
NTs
+
H R2
N OH OH
16(10 mol%)
N
O R1
NHTs R2
yield: 88-96% ee: 87-95%
R* =
SO2NPri2
7-100%de 15-42%de
Ph
SO2N(cyc-C6H11)2
25-70%de
2-70%de
O O
2-48%de
O
N S OO
RCHO DABCO
O O ROR
NEt3 MeOH
MeO2C
*R
OH
yield: 33-98%, ee: >99%
手性亲电试剂
OR1 R CHO
Peng-Fei Xu * Org. Lett. 2009, 11, 3310-3313
NO2
Ts
+
Ph
R
CF3 S
NN NHH
26
CF3 Ph
NO2 R
NHTs
71-91%ee 82-95%yield
NO2
Ts
+
Ph
R
X
NO2
Ph
R
NHTs
CF3 S
NN NHH
CF3
26
86%ee
S NN NHH 29 68%ee
手性叔胺催化剂
O
9, 10, 11
OH O Ar
O2N
N
N
OR
OR
9
HH
N HO 10
11-47%ee
21-72%ee
N N Me
11 44-75%ee
HH
N TBDMSO
12 rate ~26%ee
OH
N
Me
N
13
15-78%ee protic solvent, CH2Cl2, no reaction
PMP O+
O O
RH
HO N
O N
N H NHBoc
PMP
O S
34 (10 mol%)
O NH O
R
O
84-97%ee
O H
N
O H
N
HO N
N 34
O
N
N
H NHBoc
35
ON N H NHTf 36
O
N H HN
H N
O
CF3 CF3
Rt,76%ee
Rt,69%ee
Rt,55%ee
-30oC, 91%ee
Asymmetric Morita-Baylis-Hillman reaction
X
+
R R1
EWG R3
X
R
EWG
R3
X = O, NR2 R 3= H or other substituted group EWG = electron withdrawing group
反应历程
O PPh3
I OH O R1 *
1
O H
N Trt
2
N CHO
p-NO2C6H4 O de: 50% 3
CHO ON
de: 72% 4
PhO O
O N
nR
de > 97%
MeO
NTs
H OMe Cr(CO)3
de > 95%
5
6
O OMeH Cr(CO)3
de > 95% 7
O
O
O
O NR
单一构型的产物 8
催化不对称反应
ArCHO +
N OH N OH
17
N
N
OH
OH
18
N OH OH
19 17-19, ineffective
OH
N
+
OH
N
3%ee
N OMe N OH 85%yield, 79%ee
OH N OH
N
N
OH
OMe
5%yield, 24%ee
OH N OH
O OH N
OH
N OMe N OH
85%yield, 79%ee 20