Question 1: 10 points

Overman has reported an interesting observation for the key Heck cyclization in the synthesis of gelsemine. Changing the reaction
conditions to include a silver salt completely reverses the selectivity observed at the quaternary stereogenic carbon center that is
formed during the reaction. Provide an explanation for this additive effect. You DO NOT need to include a full mechanism, but
your explanation should include relevant, clear drawing(s) of key intermediate(s).

O
N
R

R
N
NR

Br

MeO 2C N
Br

MeO 2C N
Br

1
Conditions

MeO 2C N
Br

yield

2:3

10 mol% Pd2(dba)3, 10 eq. Et3N, toluene, 110 C

90%

89:11

10 mol% Pd2(dba)3, 2 eq. Ag3PO4, THF, 60 C

77%

3:97

Question 2: 12 points total

2a: 5 points
Unlike most rhodium acyl species, the complex below is stable to decarbonylation. Provide an explanation.

COEt
N
O

Rh

N
N

B
F2 N

CH3

2b: 7 points
Propose a detailed mechanism for the formation of the putative active species from complex 1 in Noyori's
asymmetric hydrogenation of simple ketones. If catalyst 2 is substituted for 1, will the reaction work without adding
base? Why or why not?
O

4 atm. H2 28C
.2 mol % 1, .4 mol% KOH
isopropanol

Ar2 Cl
P
Ru
P
Ar2
Cl

H2
N
N
H2

H2
Ar2 H
N
P
Ru
N
P
H2
Ar2
H
BH3

OH

Question 3: 11 points total

3a: 9 points. Propose a three-step synthesis of the natural product eau de Mallinckrodt from the aryl iodide. You
should only have to use chemistry discussed in Chem 153. You are limited to reagents which contain 4 carbons or
less, but you may use any catalyst.
O
I

eau de Mallinckrodt

3b: 2 points.

Given the complex molecular structure of eau de Mallinckrodt and its extreme toxicity, which organism do you
think it was isolated from?
a) Hao
b) Mark
c) Prof. White

Question 4: 12 points
4a: 8 points
Enol esters such as 1 are conveniently prepared via Horner-Emmons condensation as inseparable mixtures of E and Z isomers.
Catalytic hydrogenation using Du-PHOS as the chiral ligand provides the protected -hydroxy esters with excellent ee's at 100%
conversion. Provide two possible explanations for this result. Note: you DO NOT need to provide detailed mechanisms.

CO2Et
OBz
1

[(S,S)-Et-Du-Phos-Rh]+ (.4mol%)
60 psi H2, MeOH
12h

CO2Et
OBz
99.3% ee at 100%
conversion

R
P

P
R

DuPHOS

4b: 4 points
Assuming an enol ester can be separated into E and Z isomers, propose a simple experiment to distinguish between the two
possibilities you provided in part a.

Question 5: 12 points

H
n-hex

10 mol % Pd(OAc)2
600 psi CO, 3 eq. NEt 3
CH3CN, 100 C

Provide a mechanism for the carbonylative cyclization.

n-hex

Question 6: 12 points
Catalyst 1 was shown to be an active catalyst in the hydrosilylation of olefins:
Et3SiH
n-Bu

Et 3Si

1 mol % 1
CH2Cl2

n-Bu

BAr'4
(MeO)3P Co
1

The following pieces of mechanistic evidence were obtained:

1)
Et3SiD
n-Bu
1 mol % 1
CH2Cl2

Et 3Si

2) One equivalent of ethane (with respect to catalyst) is formed at the beginning of the reaction.

Propose a mechanism consistent with these observations.

Question 7: 15 points

TBSO
TBSO

2 eq. t-BuMe2SiH
50 atm CO
1 mol % Rh(acac)(CO)2
toluene, 120C

SiMe2t-Bu
TBSO
O
TBSO
95%

Please provide a mechanism for the silylcarbobicyclization.

+ H2

Question 8: 16 points
8a): 8 points As part of a synthesis of the natural product morinol I (3), you wish to access the advanced intermediate
2 via 1. Propose a 2 or 3 step synthesis of 2 from 1.
O

OH
O

H
O

O
O

O
2

O
3

SnBu3
H

8b): 8 points Supply the missing substrate or product in the following transformations:
O
10 mol% [Rh(dppe)}ClO4

O
Ph

Ph

ClCH2CH 2Cl 65C

OSiMe 2H

0.5 mol% Rh(acac)(CO)2

PhMe2SiH, CO

10 mol% Pd(PPh3)2Cl2

OTf

3 eq. LiCl, 1.2 eq. DBU

DMF 140C
1.5 mol %[(Rh(cod)bisphosphite
+

ligand) (BF4) ]
NH2

CO/H2 THF, 70C

+ H 2O