Kagan-Horner-Knowle不对称氢化反应

在膦配位的手性Rh催化剂催化下，前手性烯烃（如双键共轭的羧酸或酰胺）进行对映选择性的氢化的反应。

另外除了Rh催化剂，钛催化的反应也有报道。【Buchwald SL, J Am Chem Soc., 1993, 115, 12569】

反应实例

N-Acetyl-(R)-phenylalanine 2. The rhodium catalyst was obtained by adding (R,R)-DlOP 3 (fromdiethyl tartrarte) to a benzene solution of [RhCl(cyclooctene)2]2 under argon and stirring for 15 min. A solution of the catalyst (1 mmol in EtOH:PhH 4:1) was added under H2 to a solution of

1 (molar ratio catalyst:substrate 1:540). After hydrogenation at 1.1 bar, the solvent was evaporated, the residue was dissolved in 0.5N NaOH and the catalyst was filtered. Acidification and evaporation afforded 2 in 90% yield and 82%ee.

【Kagan HB, J Am Chem Soc., 1972, 94, 6429】

【Buchwald SL, J Am Chem Soc., 1993, 115, 12569】

相关文献

1* Horner L Angew Chem Int 1968 7 942

2* Knowles WS J Chem Soc Chem Comm 1968 1445

3* Kagan HB J Chem Soc Chem Comm 1971 481

4* Kagan HB J Am Chem Soc 1972 94 6429

5* Kagan HB J Organomet Chem 1975 90 353

6* Kagan HB Pure Appl Chem 1975 43 401

7* James BR J Organomet Chem 1985 279 31

8* Kagan HB Bull Soc Chim Fr 1988 846

9* Burgess K Tet Asymm 1991 2 613

10* Buchwald SL J Am Chem Soc 1993 115 12569

11* Kagan HB C R Acad Sci Serie Ilb 1996 322 131

12* Zhou QL Tet Asymm 2003 14 3219

13* Jerphagnon T Tet Asymm 2004 15 2101

14* de Bellefon C J Mol Cat A Chem 2007 268 205

编译自：Organic Syntheses Based On Name Reactions, 3RdEd, A. Hassner, Page 246.

相关反应

Noyori不对称氢化反应

还原反应汇总