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1
1
1.1
1.2
1.3
H3O+ O–H
O
sp3 H3O+ NH3
1.4
–C–C– sp
2p
1.5 C4H10O
(a) (b) (c)OH
OH
O
(d) +(e) (f)
OHN +
N OH
NH2
O
NH2
O
C Oδ+ δ–
(a) (b) (c)O H C Cl C Mg C N(d) (e)δ+ δ–δ+ δ– δ+δ–δ+δ–
OH OH OH OH
OO O
2
1.6 trans–1,3– (R,R) (S,S)
(R,S)
1.7
1.8
1.9
Cl
Cl
H
H
H
Cl
H
Cl
trans–1,3– cis–1,3–
Cl
Cl
H
HR R S S SR
OH
H
H
OH
CO2HHO2C
H
H
CO2H
CO2HOH
OH
(2R,3R)–
Cl
1,2–
ClCl
Cl
1,3–
ClCl
Cl
Cl
1,4–
ClCl
Cl
Cl
+NH2 NH2
–
+NH2
–
+NH2
–NH2
O
NO
OH
O
NO
OH
–
–
+ +(b)
(c)
(a) Cl Cl+–
3
(b) (d)
(c) (a) (c)
(e)
2 2.1
2.2 MeCO2H + NaOH = MeCO2Na + H2O [MeCO2H] = [MeCO2
–]
2.2 pH = pKa = 4.76
2.3
O 2 S 3
S H O H RSH ROH
2.4 N
N
O
CO
O
O
CO
O
–
–
––O
CO
O
–
–(d) H2C
OMe
+H2C
OMe
+
(e)
O
MeMe+ AlCl3
O
MeMe
AlCl3+–
NH2 NH2 NH2 NH2 NH2
_ _
_+++
4
2.5 m–MeO
p–
p–MeO
p–
p–
2.6
2.7
OH
O
MeO
COH
O
MeO+
–
–
+OH
O
O
Me
O
Me
O
OH
– –
CH2 CH2 CH2 CH2 CH2
–
– –
– –
Me
O O
Me Me
O O
Me Me
O O
Me–
– –
5
2.8
3
3.1
3.2
1 TS1 TS2
CH2 CH2 CH2 CH2 CH2
+
+ +
+ +
MeO CH2 + Cl–+
(a) +Me
CMeMe
+Me
CMe
Me
(b)
+(c)H
NHH
H
OHH
+
(d)
H
NH H
H
H
OH
++
MeO CH2
Cl
2 H2O–H O
H
H+
+ O H
C N–
C N
TS1 TS2
中間体
6
4 4.1
4.2
4.3
4.4
OH
OH
HH
HO
O
HHO
OHH OH2++
+O
OH
H
– H+
H2O
R
O
H
OH
R R
HO O+
––
R H
HO O(a)
H2O
HOH
–
+
+
R H
HO OH(b)
H OH2+
H3O+
H2O R H
HO OH2
R
O
H
H OH2+O
HR
O OH O OH2 O
HOEt
O OEt
HO OEt
+ +
+
– H2OH O
H
Et+
HOEt+ EtOH2
+
– H+
Me H
OO
Me H
OO H+
Me H
OOH+
O
H
H
HMe
OO
HO +H
HH OH2
+ H2O
HMe
OO
HO+ H
H
Me H
OHHOOH +
+Me H
OHOOH
+
7
4.5 p–
4.6
O–
4.7
N
O
H
O
O
p–
+–
δ+
N
O
H
O
O +–
+
–
NMe2 NMe2
– +
NHMe2
HNMe2
OH2
– H3O+
NMe2
OH2
O
H
+
+
+
+NHMe2
O
+
–
– Me2NH
O H
H2O H
NMe2
OH2
R
O
OH R
O
OH
H
H
H O
R'
R
O
OR'
H
R OH
HO O H
R'
R OH
HO OR'
O
R'
H
R
O
OR'
R O
HO OR'
H
H
+
+ H2O
+
+
+
+
O
R'
H
H
H O
R'+
+ H2O
O
R'
H
+ R'OH2
+
O
R'
H
8
4.8
4.9
4.10
4.11
NaBH4
R
O
OR'
OH
HR
O
OR'
H
H
H O
H
R OR'
HO OH
H2O
R OR'
HO O H
H
+
+ +
++
R
O
OH
+ R'OH
= 18O
R OR'
HO OH
H
+
H
R
O
OR'R
O
OR'
H2O+
O
OEtMe
MeO
Me OEt
MeO O
Me
O
OMe+ OEt
––
–
HAl
H
H H
R OR'
O
R OR'
H OAlH3
H2O
H3O+
R H
O
RCH2OH
+
R H
O H
––
–
HAl
OR'
H H–
R'OAlH2
NaBH4
MeOH
OO
O
OOH
O
9
LiAlH4
4.12
4.13
4.14
1) LiAlH4, Et2O
2) H3O+
OO
O
OH
OH
HO
O
O
O
–O
H
LiAlH4
O–
O
H
OH
HO
LiAlH4
H H
O
H H
O OH
H O–H
O
H O
O
+
O
H
Ph
O
H
Ph
H
H– H+
OH– –
–
–
Ph OH
HH
R' OR"
O
R R'
R O
R' OR"
R O +MgX +MgX
H3O+R R'
O
R R'
R OHR MgX
– MgX(OR")
– –R MgX
(a)
(e)
(b) (d)
(f)
PhCH2OH CH OH
Ph
Me
(c) C OH
Me
Me
Me PhCO2H
Ph MgI (+ MeH) Ph–D (C6H5D)
10
5 5.1
SN2
5.2
5.3 SN1
CF3 MeO
5.4
Br BrBr Br
> > >>
トランス
Br H
H Me
Br Me
H Hシス
HO–H H
HO Me
H Me
HO H
HO–
トランス シス
BrBr Br Br
(a) < < <
Br Br
MeO
Br
Me
Br
MeOCH2F3C
(b) < < <
11
5.5 3
5.6
5.7 SN1
6 6.1
R
H
OTsMeH
MeAcOH
Me MeH H
+
Me
O O–
H
OAcMeH
MeH
AcO MeH
MeS
R
S R
S
+
OTs
MeMe Me Me
+
HOAc OAc
Me Me
(a)
OMe
+ +
(b)
H OEt
+ +
+ +
+
12
6.2
E1
6.3
E2
6.4
(a) E1 (b) E2 E (c)
(d) F E1cB
TS
6.5
(a)
E2
(b) R H
Ph
OH H+
Ph
OH2+
Ph
+H
HH
OH2Ph + H3O+
R
PhPh
Br
H
Me
H
S
OEt
Me
Ph
Ph
H
R
PhMe
Br
H
Ph
H
R
OEt
Ph
Me
Ph
H
–
–
(1R,2S)
(1R,2R)
(E)–1,2–
(Z)–1,2–
– Br–
– EtOH
– Br–
– EtOH
+ +(a) (b) ++
(c) (d)+ + +
13
7 C C
7.1
7.2
(c) (d) (d)
7.3
Cl b
7.4
C1
7.5
H O
R
H
+ +O
R
H
+O
R
H ROH
OR + ROH2
+
(a) (b) (c)
+
Cl
OH Br
Br
Br
OMe
Br
OMe
+
Br
Br
(d)
Br
Br+
Br
Br+
1– –1–
(a) (b)
Cl
Ph
Cl
Ph
Cl
1,1– –1–
Br2trans–1,3–
HCl
Cl
H + H
Cl
Br
Br + Br
Br
MeOH
Br2 Br + BrOMe
OMe
1 2
14
1 2
Br 1 2
2 3 4
7.6
7.7
(a) s–
(d)
(b) (c) s–
(b)
(b) > (c) >> (a), (d)
7.8
+Br + Br
Br
BrBr +
MeOH
OMe+
1 2
2 MeOOMe MeO
OMe+
MeOH
3 4
CO2Me
CO2Me
Me
Me
OO
O
HH
O
O
OHH
エンド エキソ
+
O
CNCN
HH
O
HH
CNCN
Me
Me
Me
O
(a) (b)
Ph
CO2Me
(c)
(d) + e)
エンド エキソ
SO3H
+ H2O
SO3–
+ SO3H OH2
+
SO3–
H+
– H2O
15
7.9
7.10
7.11
H2PO4–H O P
O
OH
OH
+
+
+
+ HO P
O
OH
OH
—H3PO4+
(a)
OH OH OH OH OH+
– –
– ++
(b)
O O
+
–O
+
–O
+
–O
16
7.12
7.13
7.14
E
H
F
E
H
F
E
H
F
E
H
F
+
++
+
E
H
F
E
H
F
E
H
F
E
H
F+ +
+
+
E H
F
E H
F
E H
F
+
+
+
O
Br Br
O
H
Br
OH
O
Br
– H2O– Br–
–
–
–
(a) (b)CN
+
O O
Cl
(c) (d)Cl CO2H
+
O2N
HO3S
Cl
SO3H
(a)
(b) O
NO2
O2N + O
NO2
+
O2N
17
(a)
(b) ~ (d) O N
7.15
7.16 1
7 4
2 6
2
1
1
(c) O
O
(d) NH
O
O2N
O2N O
O
+
+ NH
O
NO2
NO2
(a)OMe
(c)OH
F
(b)Me
NC
O2N
(d)CMeO2N
NO2 NO2 NO2
NO2
O
EH
+
+
EH
+
EH EH
+
EH
+
EH
+
EH
+
18
2
8 8.1
EZ
8.2
8.3
E
H+
E
H
+
E
H
+
E
H+
+
E
H
E
H+
H
O
PhOH
H
PhKE
H
OH
Ph+
Ph
O
MeH– HO
Ph
O
Me
–HO H O
Me
H
Ph
O
Me
Ph
H+
(S)–3– –2–(S)(R)
– HO
O
3–
+OH
H
H
H OH2+
OH2
OH
H OH2+
OH+
+ H2O
O+ H3O+
2–
19
8.4
8.5
8.6
2
8.7
O
O
HO– O
O
O O–
O
–
O OH–
– HO–
OEt
O
EtO
OEt
O
H
O
OEt
O
OEt
O
H
OEt
OO
OEt
O
H
O OEt
– EtOH
OEt
––
–
–
–
HH
Me OEt
O
Me Me
O
Me OEt
O
Me Me
O OEt Me OEt
OEt
OO
OEtMe
Me
+
H OEt
Me
MeH
–EtO–
O
OEt–
–
–
O
H
O O
– EtOHOEt
O
OEt
O O O
H
O O– EtOH
– H2O
O O
H OH2+
OEt– – –
– OEt–
+ H3O+
20
8.8
8.9
8.10
EtO
O
OEt
O
H
EtO
O
OEt
O
O
OEt
OEtO
– EtOH
O
OEt
O
H
O
OEt
OO
OEt
O
H OH2+
– H2O
OEt–
OEt–
–
–
–
+ H3O+
(a)
O
Ph
OH
OO
OEt
OO
OEt
OO
Ph Br
NaOEt/EtOH
OEt
OO
Br
3– –2–
+NaOEt
EtOH
HCl/H2O
–CO2
Ph
Ph
OEt
OO
EtO
+Br
4–
HCl/H2OOEt
OO
EtONaOEt
EtOH
OH
O
OH
OO
HO
–CO2
(b)
NR2 O
H
NR2+
O–
H
H2OOHH2O NR2
H2O
OHHO NR2+
– R2NH
OH OH+ O OH2
+O
– H3O+
H
H2O
+
21
9
9.1
9.2
9.3
O
OMe Me
O
DMAP
N
NMeMe
+
N
NMeMe
O Me
+
H
Me
O
O
– N
NMeMe
O Me
+
H–
Me
O O
O H
R
‡
O
ORMe+ DMAP + MeCO2
–
Et3N
ROH
NH
O
Me
NHH
+
H B
NH
C
O
Me
NHH
+
HCO2–
NH
C
O
Me
NHHC-C
PLP
P P P
B
Me
O
CO2–
O
Me H
+
H
HCH2CO2
–
PLP + H3NCH2CO2–
+
O
+
ArN
H
R2NH NR2
H
O
O
+
–
NR2
H
Ar
N
O
O
–
–+H2O
H OH
– HO–
22
H+NR2
H
Ar
H2O
NO2 H
Ar
NO2
–R2NH
H2O NR2+
H
Ar
NO2
HO NR2+
+OH
H
Ar
NO2– H+
O
H
Ar
NO2
–
–
+
Ph
O
H
R2NH
H2O Ph
NR2
H
O
H
Ar
N
H H
O
H
Ar
N
NR2
Ph
NO2
Ar
O
–B
O
O
+
– BH
O
O
–
+
NR2
Ph
NO2
Ar
O NR2
Ph
NO2
Ar
O+–
HH
OH2
NR2
Ph
NO2
Ar
O+–
H
Ph
NO2
Ar
H
O–H2O NR2+
Ph
NO2
Ar
H
HO HO NR2+H
–R2NH
O
Ph
NO2
Ar
H
OH
Ph
NO2
Ar
H
HO+
O
Ph
NO2
Ar
H
H2O+
H– H3O+
23
9.4
10 C C 10.1
10.2
O
O
O
O
O
O
O
O
B
– O
O
–O
O
O
O–
O
O
HO
–
B
O
O
HO
– HO–
O
EtO
OOEt
EtO H
OOEt
H
– EtO––
–
O+ H+
OH+EtOH
OHOEt
H+ EtOH
OHOEt
+
EtO–HH
OOEt
H
H+ OOEt
– HCl
Cl
– EtOH
–
CCH
H2CN
CCH
H2CN
CCH
H2CN+
– –+
24
10.3
10.4
10.5
NCH
H2CO
O+ N
CH
H2CO
O++
– –
–
O
O
O
O
CO2Et
H H
CO2Et
O O
CO2Et
O
H OEt
O
CO2Et
OH2O
OEt–
+
– –O
O
O
OOH
–EtO–
HO
O
O C O
O
(1,5–4– –2,6–
O O–
O– O
–O O
H
H
H
OEt– O O O
O–
O
OH
–
H OEtO
H
H
OEt–
OH
O–HO–
–EtOH
H
H
O
H OO
O
OO
O
O
O
OH OEt H
O
OHO
O
H OEtHH
OOH
OEt–
–
OEt––
–
–
OEt–
–
E1cB
25
10.6
10.7
(c) Cl
(d) F
10.8
E1cB D+
E2 D+
10.9
(a) 2 (b) CF3
11 11.1
OMe
Cl
NO
O
+ –
OMe
Cl
NO
O
+ –
OMe
Cl
NO
O
+
OMe
Cl
NO
O
+
–
– ––
–
–
NH2
O2N NO2
(a) (c)
OMe
Cl NO2
(b)N
C(O)Me
(d)
SPh
NO2
Br
+ +(a) (b)
Me
CF3
NH2
NH2Me
NH2
Me
NH2
2– –1,2–
H
OH
OH
H+ H+
H
OH
OH2
H
+ – H2OH
OHH
+H
OH
H
+
H
O
H
– H+
26
11.2
11.3
11.4
11.5
CH2NH2
OH
CH2–N2
OH– N2
OH
– H+
ONaNO2, HCl
+
+
H2O
O–OHPh
Me Me+ H+
O–OH2Ph
Me Me+
OPh
Me Me+ OH2
Me Me+OH2PhO
Me Me
+OHPhO
H
Me Me
PhOH +OH
+
– H+ O
MeMe
OPh
Me Me
+
1,2–
PhOH +
H2C N N+
H2C N N– – +
(a)
+O
ClRH2C N N
– +
ClR
O H2C N N– O
CRN
N
H
+–O
CRN
N+
H H– Cl– – H+
RCO2H RCCl RCCHN2SOCl2 CH2N2
RCH2CO2H– N2
RCH=C=OH2O
RCCH
O O O
(b)
Br2
NaOH, H2O
+ HO–
NH
O
Br– HBr
– CO2
N
O
PhNH2
O
Ph Ph
NPhC
ONH2PhNHCO2–Ph
+ H+
2–
27
11.6
12
12.1
12.2
12.3
12.4
O O
H
OH
2–
C C N C C NO
COPh
O
COPh
Me
Me
Me
Me
Br
H
HBr +
Br Br
Br
+ Br
CH3CH2C CH2
CH2CH2CH2CH3
CH3CH2C CH2
H
+
H
H H CH2CH2CH2CH3
Ph
HBr
Ph + HBr
PhBr Br
Br
Ph+ Br
28
12.5
12.6
2
12.7
12.8
12.9
N
O
O
Br
H Br
+Br
+
–N
O
O
Br
H
N
OH
O
Br2
NH
O
O
+[ ]（主生成物：E/Z 混合物）Br
Br
R IBu3Sn Bu3Sn–I + R
R
SnBu3+
+
H SnBu3
+ CNR
CN
RCN + R
CN
H
過酸化物
RO OR 2 RO
ORPh H PhROH
Ph OOH
O O Ph OO
H Ph
+Ph