hiroshima题文献介绍118kondo光学活性なアシル剤を利用した非対称化

Contents光学活性なリガンドとLewis酸を利用した非対称化StrategiesfortheSynthesisofChiralCompoundsEnantioselectiveDesymmetrizationofmeso-diol

Contents光学活性なリガンドとLewis酸を利用した非対称化AsymmetricAcylationbyOpticallyActiveAcidChlorides

(2O

(2steps) OEtO

H(1eq)

(2

(2 Nara, shima,S.;Yamada,S.Tetrahedron,1980,36,AsymmetricAcylationbyOpticallyActiveAcidChlorides

O

+

pyridine,0ºCtortovernight

39%(dr=

Bu2SnO(1.1

(1.2

toluene,4AMSreflux,2hr

toluene,0ºC,1

80%(dr=95:5)T.Mukaiyama,M.;Tomioka,I.;Shimizu,M.;Chem.Lett.1984,Contents光学活性なリガンドとLewis酸を利用した非対称化EnantioselectiveDesymmetrizationbyChiralAminesNNN

+

MS4A,–78ºC,24 23XPhCOXdiamineyieldyield1234455N Oriyama,T.;Imai,K.;Hosoya,T.;Sano,T.TetrahedronLett.1998,39,EnantioselectiveDesymmetrizationbyChiralAminesNN (0.5BzCl(1.5 Et3N(1.0

+ MS4A,CH2Cl2,–78ºC,3

83%,98:2er

not

N

N

Oriyama,T.;Imai,K.;Sano,T.;Hosoya,T.TetrahedronLett.1998,39,EnantioselectiveDesymmetrizationbyaChiralPhosphine

(5-8mol%),Ac2O(1.5eq)CH2Cl2,rt

10%conv.,76:24er

66%conv.,84:16er

84%conv.,84:16er67%conv.,64:36Vedejs,E.;Daugulis,O.;Diver,S.T.J.Org.Chem.1996,61,DesymmetrizationbyaChiralDerivativeofDMAP

(1

Ac2O(1.5eq),Et3N(1.5 t-amylalcohol,0

91%,99:1

NN

NN

N

)Fe(C)

N

OFe

ca.Ruble,J.C.;Tweddell,J.;Fu,G.C.J.Org.Chem.1998,63,2794–2795.Ruble,J.C.;Fu,G.C.J.Org.Chem.1996,61,7230–7231.DesymmetrizationbyanOligopeptide O H

H t-O N (1 Ac2O(5.0eq),iPr2NEt(5.3 toluene,–40

89%,90:10erafterquenching18hr 62:38O

Mueller,C.E.;Zell,D.;Schreiner,P.R.Chem.Eur.J.2009,15,9647–9650.Shinshia,C.B.;Sunoj,R.B.Org.Lett.2009,11,3242–3245.One-potEnantioselectiveAcylationandOxidationO ON

t-O N

(1 Ac2O(5.0eq),iPr2NEt(5.3eq),toluene,–40TEMPO(0.6eq),Bu4NBr(0.3eq),mCPBA(6-8eq),rt,~1

69%,82:18

70%,94:6

97%,97:3

42%,94:6 One-potEnantioselectiveAcylationandOxidationO ON

t-O N

(1 Ac2O(5.0eq),iPr2NEt(5.3eq),toluene,–40TEMPO(0.6eq),Bu4NBr(0.3eq),mCPBA(6-8eq),rt,~1

O 6.3 EnantioselectiveCatalyticSilylation t-Bu

t-Bu(20-30

TBSCl(2.0eq),iPr2NEt(1.25 THF,–78ºC~–28

94:7

98:2

94:6

97:3

96:4

96:4

97:3

96:4

96:4

96:4 Zhao,Y.;Rodrigo,J.;Hoveyda,A.M.;Snapper,M.L.Nature,2006,443,Zhao,Y.;Mitra,A.W.;Hoveyda,A.M.;Snapper,M.L.Angew.Chem.Int.Ed.2007,46,EnantioselectiveCatalyticSilylation HO H d+ H Ot-Bucatalyst(20TBSCl(2.0eq),iPr2NEt(1.25THF,–78ºC,24

t-Bu

t-Bu

t-Bu

t-Bu

t-Bu

H

84:17 t-Bu

t-Bu

63:37

65:35

81:19NHCCatalyzedEnantioselectiveAcylation +

Br

N N Et3N(1.0eq)toluene,25ºC,12

O

O

NR N

75%,92:8O Et3N, N

N

Reynolds,N.T.;deAlaniz,J.R.;Rovis,T.J.Am.Chem.Soc.2004,126,9518NHCCatalyzedEnantioselectiveAcylation NN

(30mol%),MnOK2CO3(30mol%),18-crown-6(15mol%)protonsponge(1.0eq),CH2Cl2,–40ºC

O

R N

58%,80%O NR

NRprotonMaki,B.E.;Chan,A.;Phillips,E.M.;Scheidt,K.A.Org.Lett.2007,9,371–374.Maki,B.E.;Chan,A.;Phillips,E.M.;Scheidt,K.A.Tetrahedron2009,65,3102–3109.Contents光学活性なリガンドとLewis酸を利用した非対称化AsymmetricAcylationbyOpticallyActiveAcidChlorides

Bu2SnO(1.1toluene,4AMSreflux,2hr

COCl(1.2toluene,0ºC,1

80%(dr=95:5)T.Mukaiyama,M.;Tomioka,I.;Shimizu,M.;Chem.Lett.1984,DesymmetrizationbytheTin(II)-DiamineComplex

(1.0 CH2Cl2,0ºC,30

O

ONNN O(1.00ºC,5

+

ABBzCl(xyieldyield123

Ichikawa,J.;Asami,M.;Mukaiyama,T.Chem.Lett.1984,DesymmetrizationbytheCu(II)-BoxComplex

Cl(5

BzCl(1.0iPr2NEt(2.0eq)CH2Cl2,0ºC,

79%,97:3er

M

H M*+

M*+

H

M

H Matsumura,Y.;Maki,T.;Murakami,S.;Onomura,O.J.Am.Chem.Soc.2003,125,DesymmetrizationbytheCu(II)-BoxComplexp-TsCl(1.2eq),K2CO3(1.5catalyst(10CH2Cl2,

BzCl(1.0eq),K2CO3(1.5catalyst(10CH2Cl2,

PhNCO(1.0catalyst(10mol%)CH2Cl2,rt

A:91%,98:2B:47%,52:48C:91%,86:14

A:99%,99:1B:68%,97:3C:96%,80:20

A:99%,99:1B:89%,98:2C:88%,83:17

A:88%,99:1B:78%,98:2C:94%,85:15 NNDemizu,Y.;Matsumoto,K.;Onomura,O.;Matsumura,Y.TetrahedronLett.2007,48,DesymmetrizationbytheZn(II)-AlkoxidesComplex N

ArArN (5Et2Zn(10vinylbenzoate(5.0R toluene,–15

R94%,96:4er

98%,96:4erS

70%,92:8er

68%,69:3160%,93:7

45%,82:18

89%,91:9Trost,B.M.;Mino,T.J.Am.Chem.Soc.2003,125,DesymmetrizationbytheZn(II)-AlkoxidesComplex

O

O Et- O

R

N

R

O Zn O

O OH O O N

H ONContents光学活性なリガンドとLewis酸を利用した非対称化EnantioselectiveDesymmetrizationofmeso-diol N

N

(5Et2Zn(10vinylbenzoate(5.0eq)toluene,–20ºC,24hr

H90%,90:10

Bu4NPF6,NaHCO3

H 34%,90:10 HTrost,B.M.;Malhotra,S.;Mino,T.;Rajapaksa,N.S.Chem.Eur.J.2008,14,Danieli,D.;Lesma,G.;Macecchini,S.;Passarella,D.;Silvani,A.Tetrahedron:Asymmetry1999,10,t-EnantioselectiveDesymmetrizationofmeso-t- N1. , O