2.还原反应案例.ppt

第2章 还原反应 1. Birch 还原 2. Bouveault-Blanc 还原 3. Cannizzaro 歧化反应 4. Clemmensen 还原 5. Luche 还原 6. Meerwein-Ponndorf-Verley 还原 7. Stephen 还原 其它还原 Other Reductions？ Corey-Bakshi-Shibata (CBS) Reduction Midland Alpine Borane Reduction Wolff-Kishner Reduction 反应实例： Org. Lett. 2007, 9, 2791-2793. J. Org. Chem. 2006, 71, 840-843. J. Org. Chem. 2006, 71, 840-843. The highly stereoselect. formal total synth. of GA111 and GA112 methyl esters was accomplish. using the combination of a Pd-cat. cycloalkenyl. react. and inverse-electron demand D-A addition in the lab of Ihara. It was found the hydride red. of this ketone gave GA112 methyl ester exclusively as a single diastereomer. When it was carried out with large exs. of Al(Oi-Pr)3, both were formed, but the GA111 methyl ester was the major. Ihara, M. et al. J. Am. Chem. Soc. 2000, 122, 9036-9037. 实例 1 The absolute stereochemistry of the rutamycin antibiotics was established through asymm. synth. of the known bicyclic degradation product by Evans et al. Metal hydrides such as LiAlH4 gave only a 1:1 mixture of axial and equatorial diastereomers. The use of the Sm(II)-cat. MVP reduction gave a 98:1 mixture of diastereomers. Evans, D. A. et al. J. Org. Chem. 1990, 55, 6260-6268. 实例 2 Stephen Reduction (Stephen Aldehyde Synthesis) The preparation of aldehydes by the reduction of nitriles with the combination of SnX2/HCl in an organic solvent is known as ~. 反应通式： 反应机理：(略) In the lab of Suzuki, the synth. of several heterocycl. condensed 1,8-naphthyridine derivat. with potential antimicrobial activity was executed. The preparation of pyrazolo[3,4- b][1,8]-naphthyridines required 7-chloro-6-formyl-3-ethyl ester as the precursor that was obtained by the Stephen reduction of the corresponding aromatic nitrile. Suzuki, N. et al. Chem. Pharm. Bull. 1980, 28, 761-768. 实例 1 The stereoselect. cyanation of [1,1]-binaphthalenyl-2,2-diiodide was developed by M. Putala and co-workers using Zn(CN)2 and catalytic amounts of Pd(d