Nickel-Catalyzed Enantioselective Diboration of 1,2-Dihydropyridines: Application and Insight into the Selectivity
Michael R Berwanger1, Trevor K Kubenik1, Hao Liang1
1Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, United States.
Abstract:
1,2-Dihydropyridine was found to undergo enantioselective nickel-catalyzed 1,4-diboration with exclusive regio- and diastereoselectivity employing a monodentate chiral phosphine ligand. The products were found to undergo regioselective allylic Suzuki-Miyaura cross-coupling with various electrophiles with high diastereospecificity. Insights into 1,4-diboration regioselectivity as well as putative reaction intermediates were obtained through NMR experimentation and computational studies.
Related Concept Videos
Diels–Alder Reaction: Characteristics of Dienophiles
Characteristics of Dienophiles
Generally, the best dienophiles are alkenes containing electron-withdrawing substituents such as carbonyl, nitrile, and nitro groups. The feasibility of a Diels–Alder reaction depends...
Regioselectivity and Stereochemistry of Hydroboration
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn stereochemistry.
Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
Diels–Alder Reaction: Characteristics of Dienes
Characteristics of the diene
Conformation
The simplest example of a diene is 1,3-butadiene, an acyclic conjugated π system. At room temperature, the molecule exists as a mixture of s-cis and s-trans conformers by virtue of rotation around the carbon–carbon single bond. Although the s-trans isomer is more stable,...


![[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)