BÀI TẬP - BÀI GIẢI TỔNG HỢP HÓA HỮU CƠ LUYỆN THI HSG QUỐC GIA (tập 4 2021)

BÀI TẬP TỔNG HỢP HÓA HỮU CƠ LUYỆN THI HSG QUỐC GIA (tập 4)BÀI TẬP TỔNG HỢP HÓA HỮU CƠ LUYỆN THI HSG QUỐC GIA (tập 4)BÀI TẬP TỔNG HỢP HÓA HỮU CƠ LUYỆN THI HSG QUỐC GIA (tập 4)BÀI TẬP TỔNG HỢP HÓA HỮU CƠ LUYỆN THI HSG QUỐC GIA (tập 4)BÀI TẬP TỔNG HỢP HÓA HỮU CƠ LUYỆN THI HSG QUỐC GIA (tập 4)BÀI TẬP TỔNG HỢP HÓA HỮU CƠ LUYỆN THI HSG QUỐC GIA (tập 4)

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BÀI TẬP

TỔNG HỢP HÓA HỮU CƠ LUYỆN THI HSG QUỐC GIA (tập 4) Thạc sĩ Phạm Công Nhân

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Fukuyama Group - Group Meeting Problems

1) O2, Rose Bengal; Me2S

CH2Cl2-MeOH, –78 °C, 5 h2) CF3CO2H

CH2Cl2, rt, 14 h 62% in 2 steps

OO

O

OHNCHCl3

–20 °C, 48 h92%

SmI2 (4 eq), t-BuOH

THF

0 °C, 10 min60%

NO2 t-BuOK (in t-BuOH)

THF

0 °C to rt, 0.5 - 1 h78%

O

O OMe

OPd(dba)3•CHCl3 (2.5 mol%)

diphenylphosphinoethanemethyl acetoacetateTHF, rt

silica gel

75%

ONMe2

Li–SiMe2PhTHF, –78 °C;

–78 to –20 °C

Li O NEt2

O

Me2N

71%

OAcO

N

H COOH

Bn

Ph3P, DEADTHF, –80 °C98%

1) TFA, rt, 96%

2) KOt-Bu, MeOH, 93%

3) PhSH, DIPEA DMF, rt, quant

Trang 3

2) mCPBA

CH2Cl2, rt, 87%

3) LHMDS; PhSeCl THF, –78 °C, 88%

4) O3; Py, CH2Cl2 –78 °C, 80%

OO

MeO2C

OHH

Hdr=12:1

5) NaOMe MeOH, rt 83%

O

O2S

Cl Br

O Br

AlCl3, CH2Cl2

rt, 87%

1)

2) HS SHp-TsOH, benzenereflux, 87%

3) Zn THF-phosphate buffer

rt, 80%

4) xylene reflux, 74%

SS

HOMeO2C

OOH

MeMe

HH

NOHO

MeMe

HH

H

HNOCl

pyridine

hνEtOH

OH

CO2Me

(Me2Al)2Seanthracenetoluene

OOOH

HOHO

OO

OOOHO

1) Me2NCH(OMe)2 dichloroethane;

evaporation;

Ac2O, 100 ºC, 68%

2) LHMDS, t-BuOOH, THF, 0 ºC, 77%

Trang 4

Ph

LDA, DPPCl*, THF;

NaN3, DMF83%

1) BF3·OEt2, THF, 70%

(isolated as salt)2) 30% aq NaOH, 68%

3) H2O, THF, reflux, 82%

NO

HHO

O

HH

1) i-AmONO, t-BuOK t-BuOH, rt

o.n., 79%

2) aq NH3, NaClO MeOH-H2O

0 °C to rt

6 hr, 55-64%

3) hν dioxane-Et2O-H2O

48 hr4) CH2N2 MeOH-Et2O (3:1 v/v)

rt, 1 hr 39-41% (2 steps)

HHO

HH

CO2Me(*DPPCl = diphenyl phosphorochloride)

OCHO

OOCHO

O

O3, vinyl acetate (7 eq), –78 °C, CH2Cl2;

CH2Cl2, reflux, 12 h, a (56%), b (26%) Hexane, reflux, 12 h, a (15%), b (63%)

1) MeNO2, TritonB2) TiCl3, Et3N

OOMeMe

OH

H

NBn

OO

MeO2C Me

Trang 12

AcOH-MeOH-H2O

hν(mercury lamp)ether89% (3 steps)

NHON

H

OH

TpRu(PPh3)(MeCN)2PF6 (10 mol%)

LiOTf (20 mol%)toluenereflux, 5 h88%

Tp: tris(1-pyrazolyl)borate

+

S+

O–Ph

SN

N

O

1) Zn-Hg, conc HCl reflux, 76%

2) PdCl2, CuCl2, O2 0.2 N HCl-DMF

65 °C, 74%

3) mCPBA, TFAA

CH2Cl2, 70%

4) FeSO4, O2 AcOH

100 °C, 57%

BtCH2SPh

(Bt = benzotriazol-1-yl)

1) n-BuLi; p-CH3C6H4CO2Me THF, –78 °C to rt

2) TsNHNH2, cat Amberlyst-15 benzene, reflux

Trang 15

AcOH-MeOH-H2O

hν(mercury lamp)ether89% (3 steps)

NHON

H

OH

TpRu(PPh3)(MeCN)2PF6 (10 mol%)

LiOTf (20 mol%)toluenereflux, 5 h88%

Tp: tris(1-pyrazolyl)borate

+

S+

O–Ph

SN

N

O

1) Zn-Hg, conc HCl reflux, 76%

2) PdCl2, CuCl2, O2 0.2 N HCl-DMF

65 °C, 74%

3) mCPBA, TFAA

CH2Cl2, 70%

4) FeSO4, O2 AcOH

100 °C, 57%

BtCH2SPh

(Bt = benzotriazol-1-yl)

1) n-BuLi; p-CH3C6H4CO2Me THF, –78 °C to rt

2) TsNHNH2, cat Amberlyst-15 benzene, reflux

Trang 24

PPh3THF

45 °C, 24 h60%

H

N OEt

OOthen,

NOH

Tf2O, Pyr;

H2NCH2CH2SH

NS

rt, 3 h51%

C 18 H 16 O 3 S

O

NaHTHF-DMSO

rt, 30 min;

MeI

35 °C, 3 h90%

NPhO2S

NO2

NPhO2S

N

H CO2Et

CN CH2CO2EtDBUTHF85%

N

58%

1) NaH allyl bromide, THF2) 9-BBN, THF, rt;

NaOMe (1.2 eq);

t-BuLi, TMEDA, –30 °C to rt;

allyl bromide;

30% H2O2 aq NaOH

Trang 25

20 °C

4 days

OH

HOH

2) MeMgI (5.0 eq) toluene

rt, 30 min 60% (2 steps)

MeMeH

H

MeMeHOMe

BrBr

RhamO

COMe

1) Pd(PPh3)4, TlOEt THF-H2O, rt, 63%

2) Dess-Martin periodinane, Py

CH2Cl2, 0 °C to rt3) (CF3CH2O)2P(O)CH2CO2Me KHMDS, 18-crown-6

THF, –78 °C, 57% (2steps)4) t-AmOH, 40 °C;

PMe3, rt, 89%*

COMeBr

RhamOTBSOTBSO

HH

OH (HO)2B

Rham =

O O Me

OMe MeO

OMe

*desired : undesired = 96 : 4

CO2Et

PPh31) , THF, rt2) Br2, CHCl3, –20 °C3) DBN, benzene, reflux

CO2Et

BocN

NBocO

1) LDA, ether

0 °C, 52%

2) KH; CS2; MeI THF, 0 °C3) Bu3SnH, AIBN toluene, 100 °C 60% (2 steps)

H

CO2MeH

S L Schreiber et al., J Am Chem Soc., 101, 2331 (1989)

A Groot et al., J Org Chem., 66, 2350 (2001)

W R Roush et al., Org Lett., 4, 3157 (2002)

W Dauben et al., Tetrahedron Lett., 38, 3711 (1973)

D M Hodgson et al., J Chem Soc Perkin Trans 1, 3150 (2001)

Trang 26

Me2ClSiCH2BrDMAP, Et3N

CH2Cl2rt

Ph3SnH AIBNacrylonitrilebenzenereflux

KHCO3

H2O2MeOH / THFreflux51% (2 steps)

CNn-C5H11HO

NO

1) NaNO2, HCl, CuCl, MeOH, 0 °C to rt, 81%

2) H2C=CHCH2Si(Me2)CH2MgBr, BF3·OEt2 CuBr2-Me2S, Et2O, –78 °C to rt, 87%

O1)

toluene, rt 88%

2) toluene, reflux 98%

3) NaBH4 MeOH, 91%

4) NaH, THF;

aq.NaOH 89%

A R Katrizky et al., J C S Perkin I, 2334 (1976)

M Malacria et al., J Org Chem., 57, 3085 (1992)

Y Kita et al., Tetrahedron Lett., 26, 2351 (1973)

S M Weinreb et al., Org Lett., 3, 3507 (2001)

L E Overman et al., J Org Chem., 50, 2403 (1985)

S M Weinreb et al., J Org Chem., 53, 1116 (1988)

Trang 35

2)

3) Na, liq NH3*, 95%

(Condition for Desulfurization)

F Br

MgTHFreflux

3 h, 90%

OTBSOBr

OMe

O

MeMeO

n-Bu3SnHAIBN(cat)benzene, 80°C(75%)

O Cl

1) Tf2O (2 eq) i-Bu3N

40 ºC, 82%

2) TfOH (1 eq)

CH2Cl2 –78 ºC, 98%

3) O3; Me2S

CH2Cl2 –78 ºC, quant

MeOH (1 eq)

0 °C

then

Cl2CHOMe (1.1 eq)LiOCEt3 (1 eq)THF

0 °C to rt

ONaOH

30% H2O2EtOH-H2O

50 °C85%

AgNO3EtOH-H2O83%

H C Brown et al., J Org Chem., 40, 813 (1975)

T K Sarkar et al., Angew Chem., Int Ed., 43, 1417 (2004)

J L Mascarenas et al., Org Lett., 3, 1181 (2001)

W D Oilis et al., Chem Commun., 99 (1969)

Trang 36

F

SOCl2, Pybenzene, reflux, 1 h;

NO

Fi-Pr

MeOH

SMe

OH

H Me

1) NH2OH·HCl NaOAc, MeOH2) NaBH3CN, MeOH3) (HCHO)n, MS4A tol, reflux4) MeOSO2F, ether, 0 °C5) LAH, THF

MeNHO

HMe

N2

O

MeOMeO

hvTHF80%

N

Ns

NBn

Bn NC

CO2H

MeOH

rt, 36 hr85%

NO

CONHBnBnNsHN

toluenereflux, 18 hr65%

K Paulvannan et al., J Org Chem., 69, 1207 (2001)

R A Olofson et al., Tetrahedron, 27, 4181 (1971)

B M Stoltz et al., J Am Chem Soc., 125, 13624 (2003)

W Oppolzer et al., J Am Chem Soc., 98, 6722 (1976)公開特許公報（A）平3-279362, US Patent 5189043 A

Trang 44

OOH

DMAD (2 eq)PPh3 (1 eq)

CH2Cl2, rt, 24 h95%

80 °C, 24 h

t-BuOKt-BuOH

185 °C60%

CO2HPh

OMeOH

PhI(OAc)2allyl alcohol

CH2Cl277%

THF, –78 °C76%

KH, 18-crown-6THF, reflux97%

H2, Pd/CMeOH95%

OR

NNOOMe

MeO

MeO2CMeO2C

CO2MeDMAD (1 eq)

benzene, reflux60%

C8H10O

O

O1) acrolein, PPh3, MeOH, rt, 30 min;

NaBH4, 0 °C, 30 min;

NaOH, 0 °C, 30 min;

3 M HCl, 0 °C, 20 min 72%

2) Zn, HCl toluene

0 °C 84%

J Warkentin et al Tetrahedron Lett 40, 1483 (1999)

I Yavari et al., J Chem Res (S), 166 (1998)

S Stanchev et al., Tetrahedron Lett., 34, 6107 (1993)

J B Stothers et al., Can J Chem., 55, 4184 (1977)

Trang 45

O Cl

1)

Et3N, ether;

benzylazide xylene, reflux 70%

2) EtSH (3 eq*) NaH (3 eq*) DMF, reflux;

aq.HCl MeOH, rt 90% *theoretical amount 2 eq

ClMeO

CO2EtH

1 xs EtONa

Et2O, reflux then

solvent exchange

to benzene and reflux

2 10% HCl, reflux

Me OH

4) sat KCN in MeOH NaOMe (cat.), 85-90%

ONC

S M Roberts et al., J Chem Soc Chem Commun., 948 (1974)

BnO

NAc

ON

O

sealed tubetoluene

200 °C77%

tetracycliccompound

1) NaBH4, EtOH, rt2) TBSOTf, 2,6-lutidine

CH2Cl2, 0 °C to rt 60% (2 steps)

3) NBS, CH2Cl2

rt, 66%

4) n-Bu3SnH, AIBN benzene, reflux 91% NAc

NO

70 %

CN BnHN

MeOHrt

75 %

(1.1 eq)

Ph Li(2.5 eq)

THF-78 °C

PhOH

Org Synth., Coll Vol V1 1988, 167

L E Overman et al., J Org Chem., 50, 2403 (1985)

A K Mapp et al., J Am Chem Soc., 126, 5364 (2004)

A Padwa et al., J Org Chem., 69, 3735 (2004)

G Stork et al., J Am Chem Soc., 82, 4315 (1960)

Trang 46

MeH

Me

OHH

BF3·OEt2

Et2O–10 °C

S

OPhO

1) cyclopentadiene

hν, CH2Cl2

20 °C, 76%

2) H2, Pd-C EtOH, rt, 84%

1 eq 2 eq

catalyst A (5 mol%)BnNEt3Cl (5 mol%)

Rh2(OAc)4 (1 mol%)

CH3CN82%

OPh

Ph

S

N Ts

O Me

Ph S

N Ts Ph

S

N Ts

O Me

Ph S

N Ph Ts

p-TsOH (0.1 eq) benzene reflux

OBnOMe

P

OBnMeO N(i-Pr)2tetrazole

OOBn

OBnOMeO

O

MeO OH

OMeO

OMe OMe TsHN

HBrAcOH64%

HCHO

BF3•OEt2CHCl390%

NTsO

T Matsumoto et al., Tetrahedron Lett., 26, 873 (1985)

V K Aggarwal et al., Angew Chem., Int Ed., 40, 1430 (2001)

Z Guo et al., Org Lett., 6, 1365 (2004)

A Garcia et al., Tetrahedron Lett., 42, 665 (2001)

H Shimizu et al., Heterocycles, 22, 1025 (1984)

Trang 47

TfOH

110 °C

45 min46%

N

NHO

OO

10% H2SO4overnightrt24% (2 steps)

H

HOH(2 eq)

Ph

OHPh

H2N

1)

Et3N2) SeO2

OEt

NH •HCl

6-memberedring

1) phenol, TFA2) H2, Pd(OH)2 TFA

CO2H

NH2HO

(mixture of o- and p-)

4

MeO

NHCOPh

1) NaH, DMF, 95%

M Node et al., J Am Chem Soc., 109, 7901 (1987)

J Am Chem Soc., 124, 9199 (2002)

F Lei et al., Synlett., 1160 (2003)

D Barbry et al., Tetrahedron, 47, 47 (1991)

B Hasiak et al., Tetrahedron Lett., 31, 5769 (1990)

Y Makisumi et al., Chem Pharm Bull., 24, 770 (1976)

Trang 62

CNAr

Et3N (cat.)EtOH, rt76%

CNCNAr

NC

NH2

Ar = 4-MeOC6H4+

O

AgBF4;

OO

80 °C, 2 h

O

CN

HNO

CN

CO2Et

C O

NaHTHF74%

1) K2CO3 DMSO, 65%

2) EtOH reflux, 63%

N

NO

Et

CO2EtNC

NBr

Et

O

CO2Et+

Me3SnSnMe380°C, hv(63 %)

(OC)5Cr

OMe

Me4N 1) AcBr, CH2Cl2

–78 °C2)

OH

OMe

OMe3) , CO THF, 80 °C, 3 d4) aq HCl

OO

Trang 63

xs aq H2O2

Na2CO3 (1.5 eq)activated carbon

H2O;

HCl94%

C4H6O4

1) TsCl (1.1 eq) pyridine, 84%

2) EtONa EtOH-THF 91%

O

CO2EtHO

HO

L O Weigel et al., J Org Chem., 56, 6225 (1991)

H L Frush et al., Carbohydr Res., 72, 301 (1979)

OMeO2C Br

1) 98% H2SO4, MVK –78 °C to rt, 77%

2) THF, 0 °C, 70%

O (MeO)2P Li

1) H2, Pd/C2) t-BuOK 18-crown-6 tol, 80 °C 64% (2 steps)

NH

O

NH2OHEtOH

H+

OO

F M Dean et al., J Chem Soc, 5096 (1964)

N

O

Me

1) EtOH, 80%

2) hν (pyrex) PhH, rt, 88%

toluenereflux71%

CHOPh

CH2Cl2

PhNHOHMeCNreflux

93 %

xylenereflux67%

NH

Ph

O Yonemitsu et al., Tetrahedron Lett., 33, 1459 (1992)

O Yonemitsu et al., Chem Pharm Bull., 30, 3097 (1982)(1.3 eq)

Trang 64

•EtH

CO2EtH

N

CO2Et

OHO

benzenereflux, 14 h60%

M.P.S Ishar et al., Tetrahedron Lett., 40, 175 (1999)

Delter, A et al., J Chem Soc., Perkin Trans 1, 110, 129 (1975)

HO

RR

O

Pd(PPh3)4P(o-tolyl)3THF reflux

O

RROH

R = Me, Et, n-Bu, -(CH2)4

-Nagao, Y et al, Org Lett., 6, 2133 (2004)

mCPBA (2.3 eq)

10 °C, 30 min80%

O

O OMeO

H Nemoto et al., J Org Chem., 62, 7850 (1997)

TBSO

1) mCPBA*

CH2Cl2, 0 °C2) 10%HBF4 aq

CH2Cl2, rt 86% (2 steps)

*theoritically 1 eq

MgBr, CeCl3THF, –78 °C to rt, 74%

3)

4) PdCl2(CH3CN)2 DME, rt, 81%

O

H

α : β = 6 : 4TBSO

1)

ZnCl2, CH2Cl2 91%

Ph

Y Kita, et al., J Org Chem., 55, 1108 (1990)

Trang 72

N Nn-Bu

MeS

N CO 2 Me

N H

NHFmoc 1) Li[Me3AlSPh]

THF, 36 h2) piperidine THF, 2.5 h 71% (2 steps)

1) m-CPBA EtOAc, –78 °C, 1 h2) benzene, reflux, 18 h3) TFA, CHCl3, reflux, 1 h 70% (3 steps)

D J Hart, N A Magomedov et al., J Am Chem Soc., 123, 5892 (2001)

O PhO

OEtO

O

OOEtPh

PPh3 (1.2 eq)*

AcOEt, 110 °C(sealed tube)72%

M J Krische et al., J Am Chem Soc., 126, 4118 (2004)

Br

HOHO

TMS

Bu3Sn

SnBu 3

Pd(PPh3)4 (20 mol%)benzene

90 °C, 6 h62%

O

H

HHO

TMS(1.3 eq)

N H H

H

1)

Me3Al, toluene, –70 °C 2) Raney-Ni, H2, MeOH

MeO2C

NO2 1) phenyl thionochloroformate DMAP, pyridine

2) n-Bu3SnH, AIBN, benzene, reflux3) LiAlH4, THF, reflux

On-Bu

S E Denmark et al., Angew Chem Int Ed., 41, 4122 (2002)

* theoretical amount: >1.0 eq

N HN

N

O O

NH

Trang 73

O

CO2EtHNaOH

EtOH65%

1) LDA; MeI THF, –78 °C, 88%

CO2EtMe

B Zwanenburg et al., Tetrahedron, 47, 1495 (1991)

B Zwanenburg et al., Tetrahedron, 41, 963 (1985)

W Herndon et al., J Am Chem Soc., 114, 8394 (1992)

Cr(CO)5OMe

Ph Ph1% aq dioxane78%

PhPh

OOMe

SHO

OAcHO

1) hν, benzene, 34%

2) DIBAL, MeOH, 0 °C, 60%

3) Ac2O, Et3N, THF DMAP, 87%

OTBS 4) TBAF, MeOH-THF, 85%

5) n-Bu3P, CCl4, 92%

6) NaI, K2CO3, CH3CN

70 °C, 72%

E Vedejs et al., J Am Chem Soc., 112, 4351 (1990)

E Vedejs et al., J Org Chem., 69, 5159 (2004)

NaHTHF

1) Cl3CCOCl, Zn(Cu) THF, 0 °C

2) Al(Hg), THF-MeOH-H2O3) n-Bu3SnOTf (1.2-1.5) toluene, 50 °C

OH

H

CO2EtEtO2C

Br

1) TsCN, rt;

AcOH/H2O 63%

2) KOH; BnBr DMSO, rt 71%

3) Br2

CH2Cl2, rt quant

4) DBN, 120 °C 81%

Barry B Snider et al., J Org Chem., 50, 1983 (1985)

PhPh

OOMe

SET

Trang 74

1) ethylene glycol, H+

(protection)

2) mCPBA (epoxidation)3) LiBH4 (opening of epoxide)

1) aq HCl, THF (deprotection and )2) aq NaOH MeOH

NO

HOCN

Otetra

cycliccompoundO

N i-Pr

O

t-BuLi, DMPU, –78 to 20 °C ;

hν, –78 °C80%, >99% eePh

CONHi-PrPh

J Clayden et al., J Am Chem Soc., 125, 9278 (2003)

CHO W(CO)5·THF (10 mol%)

n-butyl vinyl etherTHFrt94%

O

OH

72 %

D F Taber et al., J Org Chem., 64, 9673 (1999)

O

CO2EtEtO2C

+

NiCl2(PPh3)2 (5 mol%)

Zn (1.2 eq), ZnCl2 (1.2 eq)MeCN, reflux58% E:Z= 71:29

Trang 79

HOHO

O

NNMeO O

Ph

OMeO2C

J Warkentin et al., Can J Chem., 75, 120 (1997)

OMeNCNC

NHBoc

Ph CO2Me

LHMDS (2.2 eq) ;

I2 (1.2 eq)THF

LiTHF–78 °Cthenrt

OSnider, B B J Org Chem., 53, 4508 (1988)

NO

CO2Me

HH

CO2Me

1)toluene, reflux2) mCPBA, CH2Cl23) CO

2Mebenzene, reflux

4) MsCl, pyridine5) DBN

benzene6) xylene reflux

40% overall yield

J J Tufariello et al., J Am Chem Soc 101, 2435 (1979)

Me

Trang 80

filtration;

Et3N (1.0 eq)

0 °C, 2 h 70%

2) Tf2O (1.1 eq)

CH2Cl2

0 °C, 1 h;

rt, 3 h 84%

3) (2 eq*) cat PdCl2(PPh3)2 Hünig base (3 eq) DMF

80 °C, 24 h 82%

N

SO2Ph

CHO

OH N

t -Bu Me

1) t-BuOK (2 eq);

O2 benzene, 50 °C 67%

dimeric compound

2) p-TsOH benzene, reflux 72%

3)

CO2Et

CO2EtEtAlCl2

CH2Cl2, rt42%

acetone-H2O3) SmI2, HMPA t-BuOH-THF

J D Kilburn et al J Chem Soc., Chem Commun., 1875 (1998)

NH

O

OMeO

SN

O

MeO

N MeCHO

CHOO

Bubbling O2TPP (sensitizer) (0.05 eq)

hν (300W)

CH2Cl2

40 °C, 90 min62%

TPP = meso-tetraphenylporphyrin

R Riguera et al J Org Chem., 65, 4671 (2000)

CHO O O

O

MeHO

(1:1 mixture)

Trang 87

Raney Niacetone65% (2 steps)

Me3OBF4;NaBH4 TEOC-Cl*

benzenert30% (3 steps)

NO

TEOC

S J Danishefsky et al J Am Chem Soc., 112, 2003 (1990)

*TEOC-Cl= 2-(trimethylsilyl)ethyl chloroformate

Y Six et al., Eur J Org Chem., 3517 (2004)

Ph

Ac

N

Ti(O-i-Pr)4 (1.5 eq)CyMgCl (4.4eq)THF

10 min90%

(n-PrCO)2OPhClreflux, 3.5 h50%

Ac2Oreflux, 50 min69%

KOHMeOHreflux, 6.5 h75%

N

O

OHEt

CH2Cl2, 0 °C;

sat NaHCO3 aq

3) t-BuOK, THF, 0 °C4) Lawesson's rgt, THF, rt5) P(OMe)3, reflux

OO

N

SO

S J Danishefsky et al., J Org Chem , 55, 831 (1990)O

OMe

OHmalonic acid (cat.)

200 °C, 48 h73%

I Farris et al., Helv Chim Acta., 87, 1601(2004)

TMSOH

O BnBr, TBAINaH

THF, 0 °C to rt78%

t-BuLiTHF-HMPA40%

BnO TMSOHC

Trang 88

T J Katz et al., J Am Chem Soc., 93, 3782 (1971)

T J Katz et al., J Am Chem Soc., 95, 2738 (1973)

toluene, 40 ºC

1 d10%

NN

N OO

Ph

Et2O/dioxane

1 h, rt60%

1) aq KOH, MeOH

1 day; reflux2) CuCl2, aq HCl, rt;

NaOH, 0 ºC 65% (2 steps)

MeLi, MeOMe– 45 ºC;

MeLi, CH2Cl2

Me2O, Et2O– 45 ºC29%

PhMeO2C

1) benzene reflux2) hν MeOH

A G Schultz et al., J Org Chem., 45, 2040 (1980)

N

O CO2Me

SPhTBSO H

NO

2) TBSOTf, lutidine

CH2Cl2 88%

3) Cl2

CH2Cl2, –78 °C 85%

4) AgBF4

CH2Cl2, –78 °C 33%

H Horikawa et al., J.C.S Chem.Com., 2527 (1995)

OH

O H

H

1) n-BuLi, TsCl2) PhSLi3) MCPBA 80% (3 steps)

Bu3SnH, AIBNtoluene, 110 °C46%

S Itoh et al., Angew Chem Int Ed., 41, 4325 (2002)

NH

CO2H

(CH2=O)n (5 eq.), (4 eq.) PhMe, 100 °C, 4 h;

Bu2SnCl2 (0.1 eq.) 78%

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