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有机习题 (215)


Fukuyama Group - Group Meeting Problems 10/03/2007
1
1) Me TIPSO 2)
Si
tBu tBu

C6D6, reflux
O2N NC

C27H56O3Si2

3) PhMgBr, THF 0 °C to

rt; 3 N aq. HCl, 77% 4) CsF, CsOH·H2O t-BuOOH, Et2O reflux, 88%

OH Ph H HO OH Me

CH2Cl2, rt; 1 N aq. HCl, 57%

K. A. Woerpel et al., J. Am. Chem. Soc., 124, 6524 (2002)

2
Chloramine-T NBS (cat.) O OMe MeCN 79% 56% 32% MgBr Et2O –30 °C to rt SnCl4 (1.0 eq) CH2Cl2 0 °C to rt 1) CBr4, PPh3 CH2Cl2 0 °C to rt, 78% 2) t-BuLi, THF –78 to 0 °C 56% Ts N

A. Armstrong et al., J. Org. Chem., 72, 8019 (2007)

3
O O O 2 eq
N NH2

O C11H10N2O2 4 N H2SO4 100 °C O M. E. Baumann et al., Helv. Chim. Acta., 67, 1897 (1984) O

AcOH 118 °C

4
OMe MeO2C CO2Me C17H14N2O3 tetracyclic compound 1) NH2NH2, DMF 80 oC 2) TsCl, Py. 3) Na2CO3 ethylene glycol 170 oC, 10 min 71% (3 steps) N H

N H

N Me

N

O CHO

MeOH, rt quant

5
Br + HS 1) KOt-Bu EtOH (20 mM) 79% 3) mCPBA CH2Cl2, 76%

V. S. Giri et al., Synth. Communications, 28, 9 (1998)

1,2-dichloromethane C19H21N3O2 "not a pyridine" relfux 54% (2 steps) N

CN

N Br

2) hν (Hg, 180 W) 4) Me2NCOCl CH2Cl2. rt; P(OMe)3 TMSCN 64% SH

Fürstner, A. et al., J. Am. Chem. Soc., 129, 12676 (2007)

Fukuyama Group - Group Meeting Problems 10/09/2007
1F
N H O 1) NH2OH?HCl NaOH EtOH, reflux 89% 2) PPA, 90 ?C ; H2O, 71% 3) LAH dioxane, reflux 65% C12H13FN2 4) Ac2O, rt, 89% 5) LAH dioxane, reflux 91% 6)
CO2Me

F N Et N H CO2Me

MeOH, rt, 75%

J. B. Hester, J. Org. Chem., 32, 3804 (1967) Voskressensky L. G. et al., Tetrahedron, 62, 12392 (2006)

2
OTMS MeLi, THF, 0 ?C;
O Ph

PhI(OAc)2, I2 CH2Cl2, 0 ?C 62% (2 steps) C15H19IO2

1) NaN3, DMSO, 24 h 2) H2, Lindlar's catalyst MeOH, 24 h syn-product 74% anti-product 71%

O NH OH Ph

BF3? OEt2, –78 ?C 30 min

G. H. Posner et al., Org. Lett., 9, 2673 (2007)

3
O TIPSO CHCl3 50% aq NaOH BnEt3NCl OMe C24H38Cl2O2Si AgBF4, MeCN reflux 81% (2 steps) OMe F. G. West et al., Org. Lett., 9, 3789 (2007) Et Cl

Et

4
pholine (2.1 equiv)

1) trichloroacetyl chloride THF, 0 °C to rt 97% C6H8Cl3NO 2) PPh3 (1.1 equiv) o-xylene, 150 °C 80% BF3?OEt2 (1.4 equiv) A (1.4 equiv) CH2Cl2, 0 °C;

3) n-BuLi (2.2 equiv) Et2O-hexane –78 °C to rt; A TMSCl (1.2 equiv) –20 °C to rt 75% O O PhO

PhO

O

KHF2 (5.0 equiv) H2O, MeCN 0 °C to rt

M. Movassaghi and E. N. Jacobsen, J. Am. Chem. Soc., 124, 2456 (2002)

5
1) LDA, TolS(O)CH2Cl THF, –78 °C O 2) Ac2O, Py, DMAP 94% (2 steps) 3) n-BuLi, 2-piperidone THF, 0 °C, 99% 5) H3PO4, AcOH-H2O reflux, 99% * n-BuLi, CH3CN: 5 eq. T. Satoh et.al., Tetrahedron, 63, 3953 (2007) 4) *n-BuLi, CH3CN THF, –78 °C to rt, 91% CN O

Fukuyama Group - Group Meeting Problems 10/17/2007
1
MeO Me O N I OTBS NTr O AgOTf·1/2benzene C6D6, rt; filt.; BnMe3N+CN? MeCN, rt 33% E. Vedejs et al., J. Org. Chem., 72, 8506 (2007) O MeO Me O N NTr OTBS

2
O Me N H CO2Et CO2Et + Cl EtOH, reflux, 2 h 38% T. P. Curran et al., J. Org. Chem., 61, 9068 (1996) Cl NaOEt (10 eq) Me N H CO2Et

3

O

Me Me N H N N H O

MTAD : MTAD, CH2Cl2 –5 ?C; evapration;

N N

N Me O

Me 110 ?C 30 min

Me N H O H N N

OH H O

O H

O2, sunlamp methylene blue, MeOH, –28 ?C, 7.5 h; Me2S;

C35H37N7O5

N Me Me H C32H34N4O2

N Me Me H C32H34N4O3 E. J. Corey et al., J. Am. Chem. Soc., 125, 5628 (2003) 1) O OEt
N Me

4

OEt Ph Ph Me N O

(CO)5W

pentane, 93%
H 2) Ph [(COD)2RhCl]2 (2.5 mol %) THF-EtOH, 69%

Ph

5
O

R. Aumann et al., Eur. J. Org. Chem., 2545 (1999)
Me N O

CHO I

H2N O

Na2SO4 THF, 50 ?C 93%

PdCl2(CH3CN)2 CHCl3, 60 ?C 99%

Pd(PPh3)4 i-Pr2NEt DMA, 100 ?C 98%

O H

Me N O

O H

H

N

M. Sasaki et al., Tetrahedron Lett., 48, 4255 (2007)

Fukuyama Group - Group Meeting Problems 10/24/2007
1
CO2Et 1) 10% NaOCl AcOH-acetone CO2Et 0 °C, 50% 2) TBSONH2 PPTS, MS4A CH2Cl2, rt, 75% C20H36O5ClNSi

NaHMDS THF, –78 °C; TBAF –78 to 0 °C 99%

DMP CH2Cl2, rt 65% EtO2C EtO2C O

Cl

S. M. Weinreb et al., J. Am. Chem. Soc., 129, 10342 (2007)

2
1) NaH (1.1 eq), THF-DMF; homoallyl bromide, 72% EtO2C N O Ph 2) hν (300 nm), benzene 81%* [Cu(PPh3)Cl]4 THF reflux EtO2C N O Ph

* 1.7:1 mixture of two diastereomers 89% (The major diastereomer was used in the next step.) D. StC. Black et al., Synthesis, 1981 (2006)

3
1)
PMBO CO2H

H EtO2C O N

OH

PPh3, DEAD THF, rt 82% 2) o-dichlorobenzene 150 °C 74% C17H21NO5

TFA-CH2Cl2, rt; MsCl, TEA, 0 °C; H2, Pd/C, MeOH, rt HO

O O H N

Brandi et al., Org. Lett., 2, 2475 (2000)

4
Bn Bn N O

CO2Et HO N Me 1) AcOH 2) MeO2C
CO2Me

Bn Bn N O

H

CO2Et CO Me 2 N CO2Me

toluene, 110 °C 59% (2 steps)

H

V. M. William et al., J. Org. Chem., 72, 3097 (2007)

5
HO 1) Pd(OAc)2 (1.5 eq) ethylvinyl ether (4 eq) NaOAc (2 eq), NaI (0.2 eq) H2C=CHCOC5H11 (20 eq) 3) (S)-BINAL-H rt, 3 h, 72% (endo:exo = 3:1) 70% 2) PPTS, EtOH 98% (exo only) 4) 0.25 N HCl THF-H2O 77% BrPPh3(CH2)4CO2H KHMDS THF, 1.5 h 54% HO
4

CO2H

C5H11 HO OH

TBSO

R. C. Larock et al., J. Am. Chem. Soc., 113, 7815 (1991)


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