Preparation and use of sterically hindered organobis(2,4,6-triisopropylphenyl)hydroborates and their polystyrene derivatives for the diastereoselective reduction of ketones

• Published in: Journal of the Chemical Society, Perkin Transactions 1 no. 19; pp. 2807 - 2812
• Main Authors: Smith, K, El-Hiti, GA, Hou, DJ, DeBoos, GA
• Format: Journal Article
• Language: English
• Published: CAMBRIDGE Royal Soc Chemistry 1999
• Subjects: Chemistry; Chemistry, Organic; Physical Sciences; Science & Technology; REAGENT; ORGANIC-SYNTHESIS; POLYMERS; CYCLOHEXANONES; POTASSIUM HYDRIDE; ADDITION-COMPOUNDS; STEREOCHEMISTRY; ALKALI-METAL HYDRIDES; ORGANOBORON GROUPS; BOROHYDRIDE
• ISSN: 0300-922X; 1364-5463
• DOI: 10.1039/a904260a

Preparations of benzyl and phenylbis(2,4,6-triisopropylphenyl)hydroborates [organoditripylhydroborates] are outlined. The lithium and potassium benzylditripylhydroborates reduce substituted cyclohexanones with diastereoselectivities comparable to those obtained with the most selective reagents known (e.g. 99% cis-4-methylcyclohexanol from 4-methylcyclohexanone). Lithium phenylditripylhydroborate also reduces ketones with significant selectivity. For example, 4-methylcyclohexanone is reduced to cis-4-methylcyclohexanol in 88% isomeric purity. Unlike with most other highly selective reagents the reactions take place at room temperature and have the additional advantage that the boron reagent can be recovered quantitatively. Coupling of Merrifield's resin with ditripylfluoroborane in the presence of lithium naphthalenide affords (ditripylborylmethyl)polystyrene. Similarly, coupling of bromopolystyrene with ditripylfluoroborane in the presence of n-BuLi affords (ditripylboryl)polystyrene. Reactions of these polymeric organoboranes with t-BuLi give the corresponding polymer-supported lithium hydroborates. Lithium ditripylhydroboratylmethylpolystyrene reduces cyclic ketones in identical fashion to its non-polymeric counterpart, giving the corresponding thermodynamically less stable alcohols in 99% or better isomeric purity. Similarly, lithium ditripylhydroboratylpolystyrene behaves like its non-polymeric counterpart and reduces 4-methylcyclohexanone to cis-4-methylcyclohexanol in 89% isomeric purity. Recovery and reuse of the organoboranes are even easier for the polymeric reagents.