REVIEM ARTICLE

 

The reduction of nitriles to aldehydes: Applications of Raney nickel/sodium hypophosphite monohydrate, of Raney nickel/formic acid, or of Raney(Ni/Al) alloy/formic acid, respectively^*

 

 

Benjamin Staskun^{I, II, **} ; Theodorus van Es^III

^ISchool of Chemistry, University of the Witwatersrand, Johannesburg, P.O. Wits 2050, South Africa.
^IIHonorary Associate, Department of Chemistry and Biomolecular Sciences, Macquarie University, Sydney, NSW 2109, Australia
^IIIDepartment of Biochemistry and Microbiology, Cook College, Rutgers University, New Brunswick, New Jersey 08903-0231, USA

 

 

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ABSTRACT

The three title reductant systems have significant advantages in generating aldehydes from nitriles. These include: the utilization of convenient hydrogen sources, namely, sodium hypophosphite monohydrate and formic acid, respectively, and of the relatively inexpensive Raney nickel and Raney (Ni/Al) alloy; the convenience of conducting the reaction(s) in aqueous media at ambient temperatures and pressures, and avoiding the use of trapping agents (except when transforming glycosyl nitriles (vide infra)) and of hydrogen cylinders. Numerous examples of the utilization of the title systems are presented (mostly from the more recent literature) that demonstrate the utility of the respective methods in transforming a solo cyano group, or when accompanied by other chemosensitive functions in a structure, to the corresponding aldehyde. Such substrates include benzonitriles, glycosyl nitriles, O-, N- and S-containing heterocyclic nitriles, aliphatic-aromatic situations, and more complex fused heterocyclic and carbocyclic scaffolds. The review reports modifications of the title methods and several notable steric effects.

Keywords: Advantages, modifications, steric effects, benzonitriles, glycosyl nitriles, O-, N- and S-containing heterocyclic nitriles, miscellaneous nitriles

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Full text available only in pdf format.

 

 

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Received 22 July 2008
Revised 28 September 2008
Accepted 20 October 2008

 

 

^* Dedicated to the memory of Professor Otto Guido Backeberg, who initiated the research on the hypophosphite/Raney nickel reduction of nitriles to aldehydes.
** To whom correspondence should be addressed. E-mail: benmina@bigpond.com.au