Biological reaction, alcohol reductive amination

A typical second step after the insertion of CO into aryl or alkenyl-Pd(II) compounds is the addition to alkenes [148]. However, allenes can also be used (as shown in the following examples) where a it-allyl-r 3-Pd-complex is formed as an intermediate which undergoes a nucleophilic substitution. Thus, Alper and coworkers [148], as well as Grigg and coworkers [149], described a Pd-catalyzed transformation of o-iodophenols and o-iodoanilines with allenes in the presence of CO. Reaction of 6/1-310 or 6/1-311 with 6/1-312 in the presence of Pd° under a CO atmosphere (1 atm) led to the chromanones 6/1-314 and quinolones 6/1-315, respectively, via the Jt-allyl-r 3-Pd-complex 6/1-313 (Scheme 6/1.82). The enones obtained can be transformed by a Michael addition with amines, followed by reduction to give y-amino alcohols. Quinolones and chromanones are of interest due to their pronounced biological activity as antibacterials [150], antifungals [151] and neurotrophic factors [152]. 

By partial hydrogenation with DIBAL, or reaction with RMgX, of O-protected cyanohydrins, metallated primary imines are formed initially. Upon protonation these can be subjected to transimination with primary amines to furnish, upon reduction, biologically interesting N-substituted amino alcohols [106,108,124,143], e.g., ephedrine, tembamide, aegeline, denopamine, and some analogs of salbutamol [144]. (1 R,2S) Aimno alcohols have been converted to (5)-amphetamines by catalytic hydrogenation of their oxazolidi-nones [108]. 

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