Keys to the Problems (2021/01/16)

Yokoshima Group – Group Meeting Problems

 Keys to the Problems (2021/01/16)

3
O O
O
Cu(OAc)2⦁H2O [Cu] Me N-H insertion
N2 Me Me
NTs N
NHTs Ts
H step 1

HO [RhⅠ]
Ph MgBr MgBr
HO Ph [RhⅠ] O Ph
O O Ph workup
Me Me
Me Me N –H2O
N N
N Ts
Ts Ts
Ts step 2

O Ph O Ph O Ph
[RhⅠ] Oxidative Reductive H
Addition H Elimination
H N Me [RhⅢ] N Me [RhⅠ] N Me
O O O
S S S
O O O
Me Me Me

O Ph
O [RhⅠ] O Me
Me N O [RhⅠ] O Me
O S N
[RhⅠ] N Me H O S
O ＜ Me
S Ph
O Me Ph
H
Me pseudo-axial pseudo-equatrial

[RhⅠ]O Ph HO Ph
Me Me workup Me Me

N N
S S
O O O O

Yokoshima Group – Group Meeting Problems

 Keys to the Problems (2021/01/16)

Yokoshima Group – Group Meeting Problems

 Keys to the Problems (2021/01/16)

5
N(n-Bu)4
Me O O
O O
N(n-Bu)4 Me Si I
I
Me
F

TMS-EBX

N(n-Bu)4 O O
O O N(n-Bu)4 O
O
I H Boc O Boc O
N N
O O
BocN N BocN N Me
Si t-Bu
OTBS O
Me
F N(n-Bu)4

N(n-Bu)4
O
N(n-Bu)4 O
O N(n-Bu)4
Boc O
N O R Boc I
I N
R
BocN N
BocN N CO2
O N(n-Bu)4
O — I
O
N(n-Bu)4

N(n-Bu)4
N(n-Bu)4 O
Boc H Boc NHBoc
N N O O
OR OR
BocN N
BocN N 1,2-hydride BocN N work-up O
O shift O
O
O O

OBn
Li
Li Li n-hexyl
O
H Boc Boc
n-BuLi N
n-Bu N OR
OR
THF, –78 °C; BocN N
BocN N O
O
O O

Li Boc Boc OR
Boc N OR N
N DMPU
OR H O
BocN N O BocN N H
BocN N O n-hexyl
n-hexyl n-hexyl
O OBn
OBn O OBn
O O
O O
Li

Boc Boc
OR
Boc N
OR BocN N
N H O
–H+
H OH BocN N
BocN N n-hexyl N OR
+H+ n-hexyl
n-hexyl H H O
O OBn BnO2C
O OBn O O
O

Boc
BocN N

n-hexyl N OR
work-up
H H O
BnO2C
O

Yokoshima Group – Group Meeting Problems