n-Butyllithium Catalyzed Selective Hydroboration of Aldehydes and Ketones

Abstract

Highly efficient and selective hydroboration of aldehydes and ketones with HBpin is achieved by using the simple and convenient n-BuLi as a catalyst. The reaction proceeds rapidly with low catalyst loading (0.1-0.5 mol %) under mild conditions. Key features include the high catalytic efficiency, exceptional functional group compatibility, ample substrate scope, and high selectivity for aldehydes over ketones. Computational studies were carried out to provide a mechanistic insight into the n-BuLi catalyzed hydroboration of aldehydes/ketones with HBpin.

n‐Butyllithium (1 mol %)‐catalyzed Hydroboration of Aldehydes and Ketones with Pinacolborane

“…Here, we report the hydroboration of aldehydes and ketones using HBpin catalyzed by 1 mol % commercial n ‐butyllithium in a batch system (Scheme ). While this manuscript was in preparation, Zhangye Zhu's group reported n ‐butyllithium‐catalyzed selective hydroboration of aldehydes and ketones, confirming the potential of the present transformation (Scheme ).…”

Lithium Bromide/HBpin: A Mild and Effective Catalytic System for the Selective Hydroboration of Aldehydes and Ketones

“…,70.46, 39.38, 29.40, 26.62, 25.86, 24.65. NMR data were in accordance with reported literature 11. Phenylmethanol (2a).CDCl 3 ) δ 139.33, 133.46, 128.79, 128.38, 64.68.…”

“…Based on the above points, Zhu's group recently reported protocols for the catalytic hydroboration of aldehydes, ketones, imines, and alkynes with n‐BuLi 4 . In addition, Wu and co‐workers demonstrated a general method for the catalytic hydroboration of aldehydes, ketones, alkynes, and alkenes with HBpin using powdered NaOH as a catalyst 5 .…”

Lithium tert‐Butoxide‐catalyzed Hydroboration of Carbonyl Compounds

“…reported the solvent‐ and catalyst‐free hydroboration of aldehydes, but this method was not feasible to other carbonyl compounds. Zhu et al . described the selective hydroboration of aldehydes and ketones using n ‐butyllithium as catalyst, thus confirming the importance of the present transformation.…”