Copper-Catalyzed Functionalization of 1,3-Dienes: Hydrofunctionalization, Borofunctionalization, and Difunctionalization

Abstract

The catalytic conversion of chemical feedstocks into products of medicinal and agricultural value is a key theme across modern synthetic chemistry. As 1,3-dienes are readily available from industrial cracking processes, there is great interest in the development of sustainable methods for the functionalization of these simple molecules. Although initial developments in this field have required precious-transition-metal catalysts, there has been a push toward the use of inexpensive, nontoxic, and more abundant copper catalysts to promote functionalization. This Perspective covers the many developments in the area of copper-catalyzed functionalization of 1,3-dienes, in particular hydrofunctionalization, borofunctionalization, and difunctionalization (e.g., diamination).

Copper‐Catalyzed Regioselective Borocarbonylative Coupling of Unactivated Alkenes with Alkyl Halides: Synthesis of β‐Boryl Ketones

“…Organoboron reagents are valuable compounds in organic chemistry and have attracted lots of attention from chemists during the past decades . Among the methodologies for their preparation, transition‐metal catalyzed borofunctionalization of alkenes offers a promising strategy with due to its potential to install two unique groups across the C−C double bonds . The obtained products are also ready for further modifications to give more complexed compounds .…”

Beyond Carbon: Enantioselective and Enantiospecific Reactions with Catalytically Generated Boryl- and Silylcopper Intermediates

“… 87 With regard to 1,3-dienes, both 1,2-addition and 1,4-addition are possible, providing the allylcopper species XXII and XXIII , respectively. 88 Alternatively, the 1,4-adduct XXIII can also be generated through the isomerization from XXIII since the 1,2-addition has been suggested to be an energetically lower pathway. 89 , 90 …”

Copper-Catalyzed Highly Enantioselective 1,4-Protoboration of Terminal 1,3-Dienes

“…Using the enantioselective 1,4-bifunctional reaction of acyclic 1,3dienes to install at least one boron group is a powerful strategy to construct chiral allylic boronate reagents, which are versatile precursors for organic synthesis. [32][33][34][35][36][37][38][39][40][41][42][43][44][45] Because of challenges, such as production of geometrical isomers of the residual double bond and possible 1,2-addition leading to achiral products, achievements with this strategy were limited to methods employing carbonyl reagents, [79][80][81][82] imines, 83,84 and boron reagents. [85][86][87] Furthermore, previous studies of 1,4-hydroboration or 1,4-protoboration focused on the construction of an asymmetric C-B bond.…”