1
a b b c a c Ally anion type Propargyl/allenyl anion type a b c a b c a b c a b c a b c a b c b =,, or C a b c a b c b = Gothelf, K. V.; Jørgensen, K. A. Chem. ev. 1998, 98, 863-909 2
itrogen in the middle Allyl anion type xygen in the middle Propargyl/allenyl anion type itrillium Betaines C itrone C Carbnyl xides C itrile xides C Azomethine Imines C Carbonyl Imines C itrile Imines C C Azomethine Ylides C C Carbonyl Ylides C C itrile Ylides Azimines itrosimines Diazonium Betaines Azoxy Compounds itrosoxides itrous xide itro Compounds zone Azides C Diazoalkenes Gothelf, K. V.; Jørgensen, K. A. Chem. ev. 1998, 98, 863-909 3
a b b c a c a b b c a b c a c Ar C D D D Ar D Gothelf, K. V.; Jørgensen, K. A. Chem. ev. 1998, 98, 863-909 4
Dipole Alkene Dipole Alkene Dipole Alkene LUM M Type I Type II Type III C C C C C Gothelf, K. V.; Jørgensen, K. A. Chem. ev. 1998, 98, 863-909 5
Dipole Alkene Alkene- Lewis acid Dipole- Lewis acid Dipole Alkene LUM M Type I Type III Gothelf, K. V.; Jørgensen, K. A. Chem. ev. 1998, 98, 863-909 6
Dipole Dipolarophile Dipolarophile- Lewis acid Dipole- Lewis acid Dipole Alkene LUM M LA Lewis acid 2 Lewis acid 2 LA X X 1 1 Stanley, L. M.; Sibi, M. P. Chem. ev. 2008, 108, 2887-2902 7
1 2 3 4 1 2 endo (trans) 3 4 1 2 exo (cis) 3 4 Endo-transition state for the Diels-Alder reaction X X Transition state for 1,3-dipolar cycloaddition 1 X 1 endo 2 exo 2 Gothelf, K. V.; Jørgensen, K. A. Chem. ev. 1998, 98, 863-909 8
1 2 3 4 1 2 4 endo (trans) 3 1 2 4 exo (cis) 3 1 3 2 4 isoxazolidine eduction 2 /Pd 2 /aney i Zn, acid and more... 1 2 3 4 β-amino alcohol 2 1 is removed in eduction step. 2 4 3 primary amine Gothelf, K. V.; Jørgensen, K. A. Chem. ev. 1998, 98, 863-909 9
1 2 3 4 1 2 4 3 1 2 4 3 endo (trans) exo (cis) Pellissier,. Tetrahedron 2007, 63, 3235-3285 10
3 C e-face PMP Si-face 3 C PMP 3 C Toluene, 110 C PMP 3 C C 3 e-face PMP Si-face Ar 3 C endo-approach exo-approach PMP 3 C PMP major 2; =Bn : 95% (dr=100:0:0:0) 3; = : 80% (dr=73:9:9:9) Alcaide, B.; Almendros, P.; Alonso, J. M.; Aly, M. F.; Pardo, C.; Sáez, E. Torres, M.. J. rg. Chem. 2002, 67, 7004-7013 11
t-bu 3 C 2 C tbu 4 C 2 C 3 toluene, 60 C, 1 day, 77% 5 6 sole adduct tbu 3 C 2 C 3 C 2 C 6 tbu 1) MsCl, TEA 2) 2, Pd/C 3 C 2 C tbu 8 enantiopure indolizidine Cordero, F. M.; Pisaneschi, F.; Gensini, M.; Goti, A.; Brandi, A. Eur. J. rg. Chem. 2002, 1941-1951 12
Ac Ac Ac Ac t-bu Ac t-bu Ac t-bu Ac Ac 9; 81%; de = 100% 4 10; 62%; de = 100% AcAc t-bu Ac Ac Stecko, S.; Paśniczek, K.; Jurczak, M.; Urbańczyk-Lipkowska, Z.; Chmielewski, M. Tetrahedron: Asymmetry 2006, 17. 68-78 13
Cl, ac 3 11 12 Cl, ac 3 13 14 15 Shing. T. K. M.; Zhong, Y. L. Tetrahedron 2001, 57, 1573-1579 14
Cl, ac 3 11 12 = Shing. T. K. M.; Zhong, Y. L. Tetrahedron 2001, 57, 1573-1579 15
Cl, ac 3 13 14 15 14 15 Shing. T. K. M.; Zhong, Y. L. Tetrahedron 2001, 57, 1573-1579 16
Cl Cl Co(III)-SbF 6 (5 mol%) -40 C, C 2 Cl 2 60 h, quant. ab 4 Et Ar 18 16 17 endo:exo= >99:1 87% ee (endo) Co SbF 6 Co(III)-SbF 6 Mita, T.; htsuki,.; Ikeno, T.; Yamada, T. rg. Lett. 2002, 15, 2457-2460 17
Cl Cl 16 17 favored Co(III)-SbF 6 (5 mol%) Ar Co -40 C, C 2 Cl 2 60 h, quant. Ar Ar Ar Ar ab 4 Et Ar 18 endo:exo= >99:1 87% ee (endo) Ar disfavored (S) () (S) (S) Ar endo adduct Ar endo adduct Mita, T.; htsuki,.; Ikeno, T.; Yamada, T. rg. Lett. 2002, 15, 2457-2460 18
Bn 19 20 Cl 4 20 mol% Bn C Bn C 70% (endo:exo=99:1) 99% ee (endo) e-face Bn C Bn 21 endo Jen, W. S.; Wiener, J. J. M.; MacMillan, D. W. C. J. Am. Chem. Soc. 2000, 122, 9874-9875 19
10 mol% 23 17 2Cl DMF- 2, -10 C 120 h ab 4 C 2 C 2 24 endo 25 exo 50% (exo:endo=97:3) 90% ee (exo) C C 24 endo C 25 exo Karlsson, S.; ögberg,. Eur. J. rg. Chem. 2003, 2782-2791 20
23 17 2Cl ab 4 DMF- 2, -10 C 120 h attack from sterically lowest hindered side attack from sterically hindered side C 2 C 2 24 endo 25 exo s-cis s-trans s-cis s-trans 2Cl 2Cl 2Cl 2Cl nitrone nitrone nitrone nitrone (E)-iminium isomers (Z)-iminium isomers Karlsson, S.; ögberg,. Eur. J. rg. Chem. 2003, 2782-2791 21
22