Fukuyama Group - Group Meeting Problems

07/04/2017

1
[Rh(COD)Cl]2
DPEphos O O
O O Me Yb(OTf)3
+ Me OMe
Me OMe Ph DCE, 70 °C
Ph
93%
dr = 47:53

Q. Kang et al., Organometallics, 36, 2323 (2017)

2
O Me O Me O O Me
O O
TsOH
+
benzene, reflux
Me Dean-Stark trap Me Me
OH
Me Me Me Me Me Me
30% 15%

J. M. Amaro-Luis et al., Tetrahedron Lett., 57, 2713 (2016)

CHO H
BnNHOH AuCl3 (2 mol%) BnN
CO2Et CO2Et
CH2Cl2, rt CH3NO2, 70 ºC
CO2Et O CO2Et
92% 82%

S. Shin et al., Angew. Chem. Int. Ed., 47, 7040 (2008)

 Fukuyama Group - Group Meeting Problems
07/08/2017

1 OTMS
O2 BF3⋅Et2O
methylene blue CH(OMe)3
Me hν MgSO4
H
CH2Cl2, –78 ºC; TiCl4 CH2Cl2, 0 ºC;
Me
thiourea, rt Et2O, –78 ºC AcBr, rt
Me
O Me O
58% (2 steps) 57% Me Br OMe
Me O

P. S. Baran et al., J. Am. Chem. Soc., 138, 7536 (2016)

TMS
2 O Et2Zn H2O2
ligand NaHCO3 n-Hex OH
Si n-Hex HO
toluene, rt; MeOH/THF, reflux;
Me Me THF, 45 ºC K2CO3, rt Me

80% (2 steps)
Ph OH
dr > 98:2
HO Ph 86% ee
Ph OH Ph

N N

Me
ligand
I. Marek et al., Angew. Chem. Int. Ed., 52, 13717 (2013)

3
Ph RhBr3⋅2H2O (10 mol%) O
N dppp (20 mol%) N
NC O Ph
THF, 120 ºC
Me NC
65%

Ph2P PPh2

dppp

I. Nakamura et al., Chem. Eur. J., 23, 7686 (2017)

 Fukuyama Group - Group Meeting Problems
07/12/2017

1
1) DIBAL
CH2Cl2, –78 °C OH OH
N SiPhMe2 Cu(acac)2 88% H

N2 toluene, 85 °C 2) Hg(O2CCF3)2
AcOH, TFA N
O 58% CHCl3, rt;
AcOOH
0 °C to rt
81%

J. A. Vanecko and F. G. West, Org. Lett., 4, 2813 (2002)

2 1)
Br

CO2Me
LHMDS
THF, –78 ºC
55% HO
(E:Z = 4:1)
O CSA, LiCl H
OTBS (de > 98%) cyclic
S N
N Mes 2) benzene sulfoximine 1,4-dioxane, MeOH
40 ºC 90 ºC
88% MeO2C
80%

R. A. Stockman et al., Angew. Chem. Int. Ed., 55, 10047 (2016)

R. A. Stockman et al., Org. Lett., 16, 6290 (2014)

1) NaOH aq.
O EtOH, rt MeCHO O Me
60% SnCl4 (20 mol%)
O
2) t-BuOK, MeI CH2Cl2, 0 °C
t-BuOH, rt
80% 83% Me
(E:Z = <1:99)
(syn:anti = <1:99)

F. Shoenebeck et al., Angew. Chem. Int. Ed., 51, 5647 (2012)

P. Shanmugam et al., Tetrahedron, 52, 7737 (1996)
H. Saito et al., Bull. Chem. Soc. Jpn., 39, 694 (1966)
 Fukuyama Group - Group Meeting Problems
07/19/2017

1
TES TES
O O
O O TiCl4 O CHO
+
CH2Cl2, –78 ºC

60%

Y. Wu et al., Chem. Eur. J., 23, 2031 (2017)

2
1) THF, –78 °C to rt;
Me2TrocCl, –78 °C;
NaBPh4, –78 °C Bpin
NMe2
+ Bpin
Li 2) CDCl3, 50 ºC

67% (2 steps)

K. Aggarwal et al., J. Am. Chem. Soc., 139, 1790 (2017)

3
Me3S+I-, n-BuLi MeS CF3
O
(CF3CO)2O (2.0 eq.) THF, –20 ºC to rt;
Ph
C12H8O3NF3
N DCM, rt Ph N
AcOH, 80 ºC
Me CO2H
Me
92%
70%

T. Kurihara et al., Chem. Pharm. Bull., 49, 461 (2001)

M. Kawase et al., Tetrahedron Lett., 53, 2782 (2012)

4
Rh2(esp)2 (2.5 mol%)
OSO2NH2 PhI(OPiv)2 O
CaO, MS4A SO2
N
CH2Cl2, rt
Ph Ph
80%
Rh2(esp)2 : Bis[rhodium(α,α,α'‚α'-tetramethyl-1,3-benzenedipropionic acid)]
M. Shi et al., Org. Lett., 19, 3584 (2017)