有机合成化学复习思考题及答案

PhCH2O OH
OH
O
54.
3
2
1 OH
R3Al R
OH OH
O
OH OH O COOMe DMSO/(CF3CO)2
55.
O OH O COOMe 84%
7
56. 57.
O
Ph2CuLi +
Et R Br H3C H
Ph
S Et CH3 H
O
O CH3 MgBr CuBr.SMe2 O
O
O CH3 74%
28.
O
H n-BuLi THF, -85oC
-
CH3
HO
H 99%
29.
O N+Me2 Ph 98%
ON+Me2 Ph 85% Ph
Ph
30.
31.
CH2COOH
PhSeCl, Et3N CH2Cl2 O SePh
O
H2O2 THF O 92%
O
4
H OH
CH2I2 Zn-Cu
H OH H 63% H
H3C H 180oC H OH 60%
3
25.
Ph (R-) H3C H CH3 Ph CH3 H CH3 Ph H3C 87% H
(R-)
CH3
26.
OH 320oC
O 90%
27.
H HO H3C H H3C H H CH CO C H 2 2 2 5 CH3 H CH3 H CH(OEt)3 H O H3C H CH2 CH3 OC2H5
H CH OH 3 CH2COOEt 18%
-72oC
Ph H O
6.
+
BrCH2COOEt
Total Yield: 84%
7.
O NaOMe HCO2Et NaOH H2O O
O CHO KNH2
-
OCHO
-
O CH3I CHO-
1
N
8.
Cl CH2 + HC Pd CH2 N
+
DMF
N
H2C
H C
I H H3C
32.
33.
OH CH3CHI2 H
O
CH3CH
Zn O H
OH H
Et2Zn
h CH3 OH
34.
N2
COOCH3 54% H
35.
CH 3CH 2 1. SOCl2 H 3C C CO2 H 2. NaN3, xylene Ph
CH3 CH2 H3C C NH 2 Ph
66%
CH3SO2O
SiMe3
SiMe3
10
二、 合成题（含逆合成分析和合成路线） 1．
CHO
TM
O CHO
2
heat
O RCO3H
H2O, H+
OH OH
NaIO4
O CHO
N H HOAc
CHO
2．
CO2Et
O
CO2Et TM O O O + CO2Et
CO2Et CH2O, R2NH, H+ O EtO2C
O CO2Et
62. 63. 64.
Ph
PhH + PhCH=CH2
95%
-
CH(COOR)2
+ CH2 CHCH3
Pd(PPh3 )2Cl2
CH2 CHCH2 CH(CO2R)2
SiMe3 C C H
D+
Ph C H C
D H
H
65.
SiMe3 1. X2 2. CH3ONa X (X = Cl, Br)
66.
58.
O
R2CuLi
R
OH
Pd(PPh3)4 THF/hexane MeO2C Me Bu
59.
MeO2C Me Br +
Bu
Al(i-Bu)2
60.
H Ph Me H Syn-addition PhBr, PdL4, Et3N H Ph Ph Me
R O
Pd(OAc)2 H Ph Ph H
61.
R-X + OH + R'3N PdLn + R'3NHX
1. H+/H2O 2. EtOH/H+
CO2Et
O
O
11
MeO
MeO
H N
OMe OMe
3．由
MeO
合成
MeO
MeO
H N O
OMe OMe
TM MeO
MeO MeO ArCH2CN
NH2
+
Cl O ArCH2CN
OMe OMe
ArCH2X
MeO MeO
HCHO HCl
MeO MeO MeO MeO
t-BuOOH VO(acac)2 O 98%
OH
50.
Ti(oPr-i)4:L-(+)-tartaric acid (2:2.4) H H R OH Ti(oPr-i)4:D-(-)-tartaric acid (2:2.4) t-BuOOH, -20oC H O H R OH t-BuOOH, -20oC H O H R OH
O O CHO + -20oC Ph
H
O OH CHO H
OMe
OMe
64% ee
20.
+ COOMe H COOMe
N
21. H3C
H
OC3H7 H
+
O2 N
N N N
-
+
O2N
N H H3C
N H OC3H7
O
22.
Me Me
H Me
OO O
23.
H D + THF
D H
24
H3C H H O H
12.
13.
O O2CCH3 O H2O2 PhSeCl Ph C CHCH2CH3 Ph C CHCH2CH3 Ph C CH=CHCH3 SePh H H2O2 , NaOH BH2 B HO +
60%
14.
BH
2
+
H3C H
CH3 H
B
2
H
+
H2O2, NaOH
HO
H 99.1% ee
15.
CH2CH2OCH3 NO2 O NO2
O +
O (CH3)2S CH2
O
81%
O + O O O CuI H /H2O MgBr
+
75. 76.
Li+
O
OH O OH
-
H O Al O OR
Li+
H O Al O OR
S-
9
R-
S-type S R' H OH O R'
R-type R R' HO H 71~99%
77.
Ph R O + Et * Al CH2 C Me H (S-)
45.
t-Bu CH3 Et H Na2Cr2O 7 HClO 4/HOAc/H2 O t-Bu OH CH3 Et
46.
OAc PhCO3H
OAc O
OH PhCO3 H
OH O
O
47.
m-CPBA
48.
n-Bu H HO
t-BuOOH VO(acac)2
n-Bu H HO 98%
O
6
49.
OH
O
O base
+ O O
14
SiMe3 + O
TiCl4 O
8
67.
t-Bu
OSiMe3 PhCHO/Ft-Bu HOCH2 H
O CHOSiMe3 Ph
68.
1. B2H6 2. H2O2, OH-
69.
H3C BH 2 + H
CH3 H
B 2
H2O2 OH-
HO
H 99.1% ee
70.
B + BrCH2CO2Et
n-BuLi
OH
OH Al-Hg R' R2 OH COO 1. KOH 2. CH2N2 CH2 R' CH2COOCH3 R2 68~95% ee
80.
S Tol
O O H (S, E)
H H R [2,3] -rearrangement C TolSO2 (S)
R 80~87%
H O B HO
H
81.
O
O
e M i O L O i L O
O
O
1
H a N
4.
︶
1) CH3CH2Br 2) H3O +
t E
5.
O CH3CH2C(CH3)3
CH3 O
e M O
e M O
i L R
2
︶
LDA
-72oC
H H3C
Zn
C(CH3)3 PhCHO OH CH3 CH2COOEt OH 82%
+
HO
H CH3 CMe3
有机合成复习思考题及答案
一、 完成下列反应
1.
O
NH3 (l.) Li
H
CH3 (CH2)3 I
H O
LiO
H
H CH2CH2CH2CH3
43%
O
OLi
LDA Et2O PhCH2 Br
O CH2Ph
42~45%
2.
3.
OSiMe3
1. R4N+F-, THF 2. PhCH2Br
O CH2Ph
89%
t-BuOK t-BuOH
Ph3P CHO 53%
CH2CO2Et
71.
Ph3P 1. THPO 2. MeOH/H+
Br-
CHO
72.
3. PCC/CH2Cl2
O O (CH3O)2P CH2COCHCH2 CH2CCH3 R base
H3C R O
73.
O + (CH3)2S CH2
O
89%
74.
CH2
2
Pd Cl H3O+ O
Cl
-
9.
N
O CH3
base N
O CH2-
RX N
O CH2R
NaBH4 -40oC N H
O CH2R
H3O+ RCH2CHO 44~47%
10.
CH2
1. Hg(OAc)2 2. NaBH4
OH CH3 99.5%
11.
OSiMe3 O 1. I2, AgOAc 2. R4N+F84% I
51.
O O O O O O OH OH NaOH/H2O t-BuOH OH NaOH/H2O t-BuOH OH
+ 2 Me2CuLi Et2O -10 C 92% Esteroselectivity
o
O O
OH OH
O O
OH OH
52.
O
CH2OH
53.
PhCH2O
3
2 1
OH
Me2CuLi Et2O, -20oC
ClKCNMeFra bibliotek MeOCN Ni/H2
HCl H2O
COOH
PCl5 MeO COCl
MeO MeO NH2
MeO
MeO MeO
H N O LiAlH4
OMe OMe
MeO MeO
H N
OMe OMe
12
4．由邻苯二酚合成丁子香酚：
OH MeO
O TM MeO MeO
OH HO
OH
OH HO base MeI OH heat MeO MeO
Ph * H (S-) + Et C R OH
Me CH2
78.
Ph * O + M O C R H (R-) M=Al, Mg H3 O+ R Ph C OH H
(R-)
79.
p CH3 C6H4
O S CH2 COO +
R' R2
t-BuMgBr O
COO R' 2 CH R S O p CH3 C6H4
OH
Br base MeO
O
5．由环戊二烯及 C3 以下有机化合物合成：
TM CO2Et
+
MeMgI
+
CO2Et
+ 1. H+ 2. H2/Pd
CO2Et CO2Et
MeMgI OH
13
6．
O
O
a correct base
O 1. NaBH4 X 2. TsCl (X = OTs) 3. Raney Ni/H 2 4. NaH O
CH2 CH2OCH3 NO2
CH2CH2OCH3 NO2
2
16.
N
+
O2N Cl NO2 H2O H+
O O2N 92%
NO2
17.
N + Br F Mg N
18.
CF3 O + PhSCH2Cl O NO2 KOH-DMSO r.t., 1 hr
CF3 O CH2SPh NO2 O
19.
Ph
H
OH
O pyridine Et3N 91% CO2CH3
36.
CO2CH3
37.
CH3 HO HCOOH (H+)
CH3 CH3
CH3
CH3 CH3
CH3
HCO2-
CH3
O OCH
38.
H OTs t-BuOK O
OH
39.
H OTs t-BuOK OH O
40.
COOH
H2 / PtO2
HOAc
COOH
5
H
41.
O R HO R
Al(i-PrO)3
O O OR
benzene
O O
OR
70%
42.
O CH3 H
H LiAlH4 THF H OH CH 3
43.
CH3 H
NH2NH2.H 2O / O2 EtOH
CH3 HH H
44.
O
O OsO2
OH
OsO4/Py/THF
O
O
H2S/H 2O
O
OH