BÀI T P CƠ CH

03, 2023

1. Suggest a arrow-pushing mechanism:

NBS

O N O CH 2Cl 2 O N O
O
20 °C, 24 h H
OH Br 96%
Br

2. Predict the products of the following reactions.

O OH
Br 2
C7H 7BrO 2
CH 2Cl 2
23 °C

O OH
Br 2
C8H 9BrO 2
CH 2Cl 2
23 °C

3. Draw each of the intermediates in the following synthetic sequence.

CO 2H i) Br 2, NaHCO 3 1) SOCl2 CO 2H
C9H11BrO 4
CO 2H ii) H 3O+ workup 2) Me 2CuLi
3) Zn, AcOH
O

4. ITrong ví d dư i đây. m t trong 2 h p ch t đã chuy n hóa thành s n ph m dư i tác d ng c a Zn, tr i qua s

hình thành tác nhân Grinha. Đó là s n ph m nào? DME là m t dung môi ph bi n: 1,2-dimethoxyethane.

Br Br
H H H H H
1 equiv. Zn
or 94% yield
DME
H H H H 85 °C, 18 h H
Br Br

5. Suggest a plausible arrow-pushing mechanism for the following reaction. Don’t worry about the
stereochemistry. (Đ ng quan tâm đ n l p th ph n ng)

Me O Me O
Ar 2.5 equiv. AcBr Ar
1 equiv. Ac2O

CH2Cl2
23 °C 83%
O AcO

1
6. Suggest a plausible arrow-pushing mechanism for both reactions below. TMEDA increases the
nucleophilicity and basicity of lithium-carbon bonds.
i) TMEDA
-30 °C, 2 h i-PrCHO
ii) i-PrCHO Li -78 °C
LiO - 78 °C LiO

N: +N
2-
TMEDA Li R Li R
+N more nucleophilic
N:
& more basic

7. Đ ng phân organoborane nào là trung gian (intermediate) trong chu i dư i dây? Suggest a plausible
arrow-pushing mechanis.
N u s ch n l c v trí ngư c l i bư c đ u tiên, s n ph m cu i là gì ?

OMs OMs OMs

BH 3 NaOH

H 2O
H H 15 °C, 15 min
H 2B H 2B

8. Suggest a plausible arrow-pushing mechanism for the following reaction.

cat.
p-TolSO 3H O
OH 96%
toluene
CH3O 111 °C, 1.5 h

9. Suggest a plausible arrow-pushing mechanism for the following reaction:

HO OMOM t-BuO -
H
t-BuOH O
81%
MsO
OMOM

10. Suggest a plausible arrow-pushing mechanism for the following reaction.

O OH BF 3•Et 2O O O
N N 93%
Bn OH MeCN Bn N
23 °C, 16 h

2
11. Xác đ nh l p th s n ph m:
Note: HMPA is a (carcinogenic) t o ra ph c chelates lithium m nh m .
O MeLi OH
O-
OTBDPS OTBDPS
R
HMPA/ether
R +P = HMPA
O O O O Me 2N NMe 2
-85 °C, 1 h NMe 2

12. Hai đ ng phân sau đư c t o ra v i t l 7:1 . Assign the major and minor diastereomers.

Li
i)
O Me OH Me OH
THF, -78 °C

OSiPh 2t-Bu ii) TBAF OH OH

69% (7:1)

13. Suggest a plausible arrow-pushing mechanism for the following reaction.:

OCH3
O O
Br 2 O

t-Bu t-Bu
O CH 2Cl 2/AcOH O
0 - 23 °C Br
H 78% H
O O
O O