Recent Advances in Nucleophilic Addition Reactions of Organoboronic Acids and Their Derivatives to Unsaturated CN Functionalities

Reactivity and Synthetic Applications of Multicomponent Petasis Reactions

“…The PR has been developed as a powerful multicomponent transformation owing to several attractive features, such as a wide scope and relatively diverse variability for each of the three PR components, compatibility with various secondary transformations, and high stereoselectivity for the formation of functional amine products, together with other merits including mild and robust reaction conditions, ready availability of starting substrates, flexible scalability ranging from microscale to gram scale, and an atom-economical nature (Figure ). In addition to the versatile synthetic utility, the biologically relevant properties of many products make the PR a powerful tool in probe compound development and drug development. − The topic has been reviewed on several occasions in both book chapters − and journal articles, ,, either as a comprehensive summary, such as the chapter in 2005 by Petasis and the full compilation in 2010 by Candeias and coworkers, or a part of a broader topic, such as the nucleophilic addition of boronic acids and derivatives to imines, asymmetric MCRs, and stereocontrolled cascade reactions …”

Tertiary amine synthesis via reductive coupling of amides with Grignard reagents

“…Classical synthetic routes typically rely on C–N bond forming reactions such as amine-carbonyl reductive amination, amine alkylation and C–N cross-coupling. 1 , 2 However, amine synthesis through carbon–carbon bond formation alpha to nitrogen offers complementarity especially for accessing α-branched products, and, as such, the synthetic utility of the Petasis–Mannich reaction 3 as well as the directed amine lithiation/functionalisation approach of Beak, Hoppe, and others, are well-documented. 4 Furthermore, α-functionalisation of amines via radical intermediates produced through photoredox activation have recently been achieved.…”

Transition-Metal-Free Stereospecific Cross-Coupling with Alkenylboronic Acids as Nucleophiles

“…Due to relatively low nucleophilicity, aryl/alkenylboronic acids are less reported as pure nucleophiles, but more rather as coupling reagents in transition-metal catalyzed Suzuki–Miyaura cross-coupling reactions . One of most known examples of aryl/alkenylboronic acids as pure nucleophiles is the Petasis borono-Mannich reaction, where the addition of an aryl/alkenylboronic acid or equivalent to a CN π bond takes place. Accordingly, the nucleophilic addition of aryl/alkenylboronic acids or equivalents to π systems such as CN, CO, and CC double bonds are most reported, , whereas little study is available on nucleophilic substitution of aryl/alkenylboronic acids to tetravalent (sp 3 ) carbons.…”