Synthetic Transformations of Organic Nitriles

These direct reactions on nitrile functions often produce simple transformations. It is the potential for further transformation of the immediate products, especially in association with nearby functionality, that gives the chemistry its ability to access a wide range of synthetic targets. 

Reduction of [ CJnitriles with metal hydrides such as DIBAL and LiH[ Al(OEt)3] provides labeled imines, which can be readily hydrolyzed to [l- C]aldehydes. With SnCla and 

imine products hydrolyze to [l- Claldehydes during workup, whereas with Raney nickel and NaH2P02 in aqueous acetic acid or Raney nickel and formic acid [1- C]- 

Reaction conditions 1. Raney-Ni, aq. NaHP04, AcOH, pyridine 2. NaBH(OAc)3, CH2CI2 3. DIBAL, hexane 4. 2N NaOH, acetone 5. H2SO4, MeN02 6. DIBAL, toluene 7. aq. NH3 8. DIBAL, toluene 9. morpholine, EtOH reflux 10. DIBAL, hexane 11a. H2NOH HCI, Na2C03, H20,b. NCS, py, CH2CI2 

The palladium-catalyzed hemihydrogenation of protected 2-deoxy-o-aldonic acid [ C]-nitriles has become an established procedure for the preparation of 2-deoxy-D-[l- C]-glucose (32), 2-deoxy-D-[l- C]ribose and various 5-deoxy-[l- C]pentoses .  

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