SR_Syn01
OH
CO2Et
OH
SR_Syn02
O
O
SR_Syn03
O
Br
O
H
SR_Syn04
O
HO
N
O
30.01
156/158
↓ I Mgo + R-C(=O)H (what is “R”…good question)
wirh D2 O
↓ i. PCC. ii. Zn(Hg), HCl
TMS
220
210
200
1 90
18 0
170
160
150
140
130
120
1 10
↓ i. NBS, hv. ii. Mgo. iii. CO2
10 0
90
80
70
60
50
40
30
20
10
0
30.01c
30.02
From the preceding problem, write a detailed, stepwise mechanism for the reaction of 30.01c with
NBS/hv. What is the product of this reaction and why is it formed…and not other possibilities?
30.03
Upon treating compound 30.03 (solve this spectral problem to know the structure of 30.03) with an
acid catalyst, a rearrangement occurs. How and why does this happen?
TMS
220
210
200
1 90
18 0
170
160
150
140
130
120
1 10
10 0
90
80
70
60
50
40
30
20
10
0
30.04
CHO
1.
2.
3.
4.
5.
CH 3 CH 2CHO, H +
H2 , Pd-C
CrO3 , H 2O, H 2SO4
CH 2 N2
MeMgBr (xs), THF
30.05
NH 2
O
H
31.01
X with D 2O
↓ 1. SOCl2. 2. NH3 (excess)
↓ 1. LiAlH4. 2. CH3CH2C(=O)Cl, Et3N.
TMS
220
210
200
1 90
18 0
170
160
150
140
130
↓ 1. MCPBA. 2. LiAlH4.
120
1 10
10 0
90
80
70
60
50
40
30
20
10
0
31.02
with D 2 O
TMS
220
210
200
1 90
18 0
170
160
150
140
130
120
1 10
10 0
90
80
70
60
50
40
30
20
10
0
31.03
O
31.04
O
O
32.01
TMS
220
210
200
1 90
18 0
170
160
150
140
130
120
1 10
10 0
90
80
70
60
50
40
30
↓ 1. NaOEt, EtOH, Δ. 2. NaOH, H2O, Δ. 3. H3O+, Δ.
↓ 1. (EtO)2P(=O)CH2CO2Et, NaH. 2. NaOH, H2O, Δ.
X with D 2O
↓ 1. SOCl2. 2. pyrrolidine (= C4H9N).
20
10
0
32.02
↓ 1. NaOH, H2O, Δ. 2. CrO3, H2SO4, H2O.
↓ 1. SOCl2. 2. CH2=CHCH2NH2, pyridine.
TMS
220
210
200
1 90
18 0
170
160
150
140
130
↓ 1. MCPBA. 2. LiAlH4.
with D2O
120
1 10
10 0
90
80
70
60
50
40
30
20
10
0
32.03 (additional info...prepared via a Robinson annulation)
TMS
220
210
200
1 90
18 0
170
160
150
140
130
120
1 10
10 0
90
80
70
60
50
40
30
224
20
10
0
32.04
1.
2.
3.
4.
32.05
O
O
Br
O
KOH (-H 2O)
Et2 CuLi
Ph3 P=CH2
CH 2 I2 , Zn(Cu)