日本东京大学Fukuyama组10年组会2012有机反应机理习题(适合研究生),八,题目

1) TFA CH2Cl2, rt 70 % 2) MsCl, Et3N CH2Cl2, 0 ºC; evap.; H2, Pd/C MeOH, rt, 20%
O HO H N O
A. Brandi et al., Org. Lett., 2, 2475 (2000)
4
EtO2C NO2 (2.0 eq) Ph N Ph BnNH2 reflux 86% O O BnHN O N NHBn
Cl
O
Me
tricyclic compound (except Ph) 4)
i-Pr2NEt CH2Cl2, rt 92%
O t-amyl O O Ph
Me Me O N N
OTBDPS
t-BuPh, 120 ºC 62%
H O
A. G. Myers et al., J. Am. Chem. Soc., 127, 5342 (2005)
O P O O Cl
CuSO4·5H2O (15 mol%) 1,10-phenanthroline (30 mol%) K3PO4
Br Ph
O O P N O toluene, 135 °C 84% Ph
toluene, 60 °C 47%
Et3N, CH2Cl2 0 °C to rt 92% (2 steps)
H Me OH O OBn
3
Cl Cl OMe
D. Romo et al., J. Org. Chem., 72, 9053 (2007)
TMS
Br Ph
(1.2 eq.) n-BuLi (2.5 eq.) THF, –80 °C 81%
H2SO4 MeOH, 30 °C
O
TMS
Ph 83% M. Segi et al., Tetrahedron Lett., 51, 1294 (2010)
S. Umezawa et al., Bull. Chem. Soc. Jpn., 36, 1150 (1963)
Fukuyama Group - Group Meeting Problems 08/22/2012
1
Ph TsN
TsN3, CuI, TBAI, K2CO3 CH2Cl2, rt; neutral Al2O3 77% TsN
2
O Me OBn H
Me
OTES
S (E/Z =4/1)
N
ZnCl2 CH2Cl2, 23 ºC 83% (dr > 19:1)
O3 CH2Cl2, –78 ºC; PPh3 89%
IR 1827, 1714 cm–1
TESOTf Et3SiH CH2Cl2 –78 to 0 ºC 66%
Me
H
O
90 °C; Me2NH (2.2 eq), 0 °C to rt; N cyclopentadiene, NaOMe, 125 °C 51-59% K-P. Meinhardt et al., Org. Synth., 62, 134 (1984)
2
O N O
1) NH2NH2 CH2Cl2, rt 2)
O
Ph
Y.-Q. Tu et al., Chem. Sci., 3, 1975 (2012)
2
Me Me O H2N O NBoc OTBDPS 1) PhSH, Et3N THF, 70 ºC 95% 2) TMSOTf, 2,6-lutidine CH2Cl2, –78 to 0 ºC 98%
Leabharlann Baidu
3)
4
Me AuCl3 (6 mol%) O O CH3CN, rt 90% OH Me O
A. S. K. Hashmi et al., Chem. Eur. J., 3703 (2008)
Fukuyama Group - Group Meeting Problems 08/08/2012
1
NO2 O2N Cl
3
HO O Br2 (theoretically 3 eq.) Sodium tetraborate THF-NaOH aq. 0 °C 13% O O O
O
T. Rosenau et al., Eur. J. Org. Chem., 2011, 3036 (2011)
4
Me Me2Si OH [Rh(OH)(cod)2] (2.5 mol%) Ligand (6 mol%) mesitylene, 100 °C 75%, 99%ee, dr=19:1 1) TsOH (5 mol%) CH2Cl2, 23 °C 2) toluene, 80 °C 71% (2 steps) Me H H SiMe2
K.A. DeKorver et al., Org. Lett., 14, 1768 (2012)
3
H EtO2C O N OH
CO2H 1) PMBO PPh3, DEAD THF, 0 ºC, 82%
2) o-dichlorobenzene 150 ºC, 73%
tricyclic compound (except for PMB group)
Fukuyama Group - Group Meeting Problems 08/01/2012
1
O Me CONHBn Me CO2Me hυ THF, rt; evap. conc. H2SO4 THF-MeOH rt 50% Me Me O O
O
O NHBn OMe
P. S. Baran et al., Angew. Chem. Int. Ed., 45, 249 (2006)
F F F F O O O O PPh2 PPh2
Ligand
N. Cramer et al., Angew. Chem. Int. Ed., 49, 10163 (2010)