第五章:不对称 Diels- Alder反应 引言 手性亲双烯体 手性双烯体 双不对称反应 手性催化剂 杂 Diels-Alder反应 分子内 Diels-Alder反应 逆 Diels-Ader
第五章：不对称Diels-Alder反应 •引言 •手性亲双烯体 •手性双烯体 •双不对称反应 •手性催化剂 •杂Diels-Alder反应 •分子内Diels-Alder反应 •逆Diels-Alder
1.引言 HOMO LUMO Orientation of substituents R Major R R R R R Minol
1. 引言 HOMO LUMO 1) Orientation of substituents R R' R' R R R' R' R Major Minor
e) Favorite property of substituents R-electron donating; R-electron withdrawing 3)Stereochemistry of substituents on alkene R R R CIS R R R R R R Trans R R R
2) Favorite property of substituents: R-electron donating; R'-electron withdrawing 3) Stereochemistry of substituents on alkene R R' R' R R R' R' R R' R R' R cis Trans
Stereochemistry of whole cycle additionl R R in front major behind R R R R in front behind minor
4) Stereochemistry of whole cycle addition R R' O R R' O major in front behind minor R R' O R R' O in front behind
R behind in front major R R behind in front minor
R R' O major R R' O behind in front R R' O minor R R' O behind in front
2.手性亲双烯体 2.1手性酯 OMe ACl3(1.1e.q)-30 R*O2C CO2Me Ph 200 Ph ● COmE Ticl4(1.5e.q),-20C COmE endo exo=8: 1 19
2. 手性亲双烯体 2.1 手性酯 O O Ph O OMe O AlCl3 (1.1e.q) -30 oC R*O CO2Me 2C R*O2C CO2Me 200 : 1 Ph O O TiCl 4 (1.5e.q), -20 oC CO2Me CO2Me endo:exo=8:1 19 : 1
B OR* B Br 0.75e.q TICl4 CO,R* CO2R CH2Cl2, -240C ROH=A. endo exo=54: 1 98 ROH=B. endo exo=38: 1 2 98 HO、 HO N-CH3 A B
Br OR* O 0.75e.q TiCl 4 CH2 Cl 2 , -24 oC CO2 R* Br CO2 R* Br R 98 : 2 *OH=A, endo:exo=54:1 R*OH=B, endo:exo=38:1 2 : 98 O O HO N O HO CH3 A B
2.2手性酰胺 R R Poo Bno Bno major mIno Bno R R R Ph Me Ph h maor minor
2.2 手性酰胺 R N O O BnO O R O N O BnO O R O N O O BnO major minor R N O O O Me Ph R O N O O Me Ph R O N O O Me Ph major minor
Et2AICl N CH2Cl2 t- Bu endo: exo=>97: 3 96%ee
N O O t - Bu + Et 2 AlCl CH2 Cl 2 N O O t - Bu endo:exo=>97:3 96%e.e
2.3手性不饱和酮 H OH Znc, -200C OH O endo exo=15: 1 >100 OH OH ZnCl2, -20oC OH H H endo exo=15: 1 >100
2.3 手性不饱和酮 O OH H ZnCl 2 , -20 oC OH H O OH H O endo:exo=15:1 >100 : 1 O OH H ZnCl 2 , -20 oC OH H O OH H O endo:exo=15:1 >100 : 1