Hydride donor reagents table

A large amount of data has been accumulated on the stereoselectivity of reduction of cyclic ketones.81 Table 5.4 compares the stereochemistry of reduction of several ketones by hydride donors of increasing seric bulk. The trends in the table illustrate the increasing importance of steric approach control as both the hydride reagent and the ketone become more highly substituted. The alkyl-substituted borohydrides have especially high selectivity for the least hindered direction of approach. 

Tetraalkylborates are mild and selective alkylation reagents [186, 187], and they are commonly considered as sources of nucleophilic alkyl groups (R ) just as borohy-drides are depicted as hydride (H ) sources. However, since organoborates represent excellent electron donors (see Table 5, Section 2.2.1), the question arises as to what role electron donor-acceptor interactions play in the nucleophilic alkyl transfer. Phenyl- and alkyl-substituted borate ions form highly colored charge-transfer salts with a variety of cationic pyridinium acceptors [65], which represent ideal substrates to probe the methyl-transfer mechanisms. Most pyridinium borate salts are quite stable in crystalline form (see for example Figure 5C), but decompose rapidly when dissolved in tetrahydrofuran to yield methylated hydropyridines (Eq. 65). 

The donor-acceptor acyl chloride-aluminium chloride complex is not only an electrophilic reagent but also a hydride ion acceptor (oxidizing reagent). The best hydride donors are the saturated hydrocarbons, specially those containing a tertiary carbon atom. The acylation of cyclohexane is an old and well-known reaction giving acetyl-methyl-cyclopentene and/or -cyclopentane. 26,27 the yields are low because the solvent used was either cyclohexane itself or small quantities of chloroform. in our hands, we found that the reaction carried out in methylene chloride solution ( IM) led to the l-acetyl-2-methylcyclopentene and l,3-diacetyl-2-methylcyclopentene Z in good yields. A cleaner reaction also occurred from methylcyclopentane. The ratio of ys could be changed by modification of the reaction conditions (see Table 1) (overall yields of the hydrocarbons functionalization were around 75-80 %). 

---