分子式催化剂以不同溶剂催化Husigen-cycloaddition(I).docVIP

分子式催化劑以不同溶劑催化Husigen-cycloaddition (I) Condition: Benzyl azide = 1 mmol, phenyl acetylene = 1.2 mmol. solvent = 0.25 mL, 27 oC, 1 mol% (hmim)CuI. Yield determined by 1H NMR Solvent Time yield Time yield H2O 10 min 40 % CH2Cl2 10 min 99 % 3 min 99 % CHCl3 10 min 99 % 3 min 99 % THF 10 min 99 % 3 min 67% Acetone 10 min 99 % 3 min 86 % MeOH 10 min 12 % CH3CN 10 min 99 % 3 min 99 % DMSO 10 min 22 % Neat 10 min 99 % 3 min 99 % Solvent Time yield Time yield CH3CN 10 min 27% 30 min 43% Neat 10 min 47 % 30 min 99 % 分子式催化劑催化phenyl acetylene 的Husigen-cycloaddition (II) Condition: RT, 1 mol % cat. loading, CH3CN 0.2 mL azide alkyne Time Yield Time Yield 10 min 70 % 30 min 99% 10 min 59 % 30 min 97 % 10 min 99 % 3 min 99 % 10 min 34 %a 10 min 17 % 4 hr 60 % 10 min 95 % 3 min 32 % 10 min 99 % 3 min 99 % a average conversion for twice 分子式催化劑催化nonyne的Husigen-cycloaddition (III) Condition: RT, 1 mol % cat. Loading, CH3CN 0.2 mL azide alkyne Time Yield Time Yield 30 min 36 % 2 hr 91 % 30 min 24 % 2.5 hr 99 % 10 min 13 % 30 min 91 % 30 min 30 % 1.5 hr 97 % 30 min 25 % 4 hr 92 % 30 min 44 % 1.5 hr 99 % 30 min 44 % 1.5 hr 99 % 分子式催化劑催化phenyl acetylene 的Husigen-cycloaddition (II) Condition: RT, 1 mol % cat. Loading, Neat azide alkyne Time Yield Time Yield 10 min 99 % 10 min 99 % 10 min 99 % 3 min 99% 10 min 99 % 3 min 43 % 10 min 99 % 3 min 99% 分子式催化劑催化nonyne的Husigen-cycloaddition (III) Condition: RT, 1 mol % cat. Loading, neat azide Alkyne Time Yield Time Yield 30 min 36 % 1.5 hr 99 % 30 min 24 % 2 hr 97 % 30 min 67 % 1 hr 99 % 30 min 38 % 1 hr 88 % 30 min 22 % 4 hr 94 % 30 min 55 % 1 hr 97 % 30 min 89 % 1 hr 99 % Azide Time (min) Conv. (%) TOF (h-1) Azide Time (min) Conv. (%) TOF (h-1) 10 99 600 3 99 2000 10 99 600 10 99 600 10 99 600 3 99 2000 3 99 2000 Azide Time (h) Conv. (%) TOF (h-1) Azide Time (h) Conv. (%