不对称催化烯烃卤化反应.ppt

1. Introduction 2. Chiral Lewis Base Catalysis 3. Chiral Ion Pairing Catalysis 4. Hydrogen Bonding 5. Lewis Acid Catalysis 6. Conclusion 第 1 页 / 共 24 页 1. Introduction R 1 R 1 X R 1 R 1 X HNu -H + R 1 R 1 Nu X X Equiv es(%) Br 0 100 Br Na 1.0 28 Br 1.0 81 Cl nBu 4 N 1.0 100 Prn nPr OR X Prn nPr MOAc (2.0 equiv) HFIP or HFIP/CH 2 Cl 2 ,RT Prn nPr OAc X M Na nBu 4 N olefin-to-olefin transfer 第 2 页 / 共 24 页 Catalysis model Scott E. Denmark, Angew. Chem. Int. Ed . 2012 , 51 , 10938 – 10953 X X X X X LB* chiral Lewis base or Y* Y Cat* chiral counterion and anion binding Z H *Cat hydrogen bonding B: LA* chiral Lewis acid 第 3 页 / 共 24 页 2. Chiral Lewis Base Catalysis R NIS(1.1 eq), promoter(1 eq) toluene , -40 o C, 24 h ClSO 3 H iPrNO 2 ,-78 o C I H R R=p-Me, 57% yield, 95% ee R=p-OMe,58%yield,91% ee SiPh 3 O O SiPh 3 P NH P h K. Ishihara, Nature 2007 , 445 , 900 – 903. SiPh 3 O O SiPh 3 P NH Ph I N O O 第 4 页 / 共 24 页 Ar TMS (DHQ)PYR(10 mol%) K 2 CO 3 (6 equiv),NFSI(1.2 equiv) MeCN, -20 or 40 o C F Ar up to 81% yield,95% ee N. Shibata, Angew. Chem.Int. Ed . 2008 , 47 , 4157 - 4161. N R 2 XH R 1 (DHQ) 2 PHAL (0.2 equiv) NFSI(1.2 equiv), K 2 CO 3 (6 equiv) acetone, -78 o C N R 2 R 1 X F H N N O N OMe N N MeO N O (DHQ) 2 PHAL up to 95% yield, 92? V. Gouverneur, Angew. Chem. Int. Ed . 2011 , 50 , 8105 – 8109 第 5 页 / 共 24 页 R 1 R 2 R 2 OH O cat (15mol%), 15 mol% I 2 I + source(1-2 equiv), toluene -80 o C, 5 days O O R 1 I R 2 R 2 up to 96% yield, 96% ee CF 3 F 3 C N H N H O N(C 5 H 11 ) 2 N O O I F Cat I + source E. N. Jacobsen, Angew. Chem. Int. Ed. 2010 , 49 , 7332 – 7335 第 6 页 / 共 24 页 3. Chiral Ion Pairing Catalysis OH HO cat (20mol%) NBS or N-iodo-2-pyrrolidone CH 2 Cl 2 , 0 o C, 4 A M.S. 2-12h OH O X O O P O O SiPh 3 SiPh 3 cat Na up to 89% yield,71? R. Fr? hlich, Org. Lett . 2011 , 13, 860 – 863. L. X. Gao, J. Org. Chem. 2004 , 69 , 2874-2876 O Ph OH Cat (30mol%), I 2 CH 2 Cl 2 ,H 2 O, NaHCO 3 , 0 o C O O