Industrially applied and relevant transformations of 1,3-butadiene using homogeneous catalysts

Abstract

In recent decades, the use of 1,3-butadiene as a comparably cheap and abundant raw material for new applications has attracted more and more interest, specifically in the chemical industry. The...

Understanding the Regiodivergence between Hydroarylation and Trifluoromethylarylation of 1,3-Dienes Using Anilines in HFIP

“…Olefins are one of the most abundant species within chemical feedstock, such that ethylene and propylene are the basic building blocks in the chemical industry. Their conjugated diene counterparts (i.e., 1,3-dienes) are versatile and valuable chemical species that can be used as two-carbon or four-carbon synthons; 1,3-butadiene production is in the million metric tons every year and constantly increasing. − Although conjugated dienes feature a relatively simple and easily accessible structure, their chemical properties go far beyond those of simple olefins. While their reactivity has been extensively studied and it represents a rich area of research with continuous innovations, mainly using transition metal catalysis, competitive metal-free approaches are still lacking. − From all of the possible strategies, the hydrofunctionalization of 1,3-dienes represents the most basic transformation from a chemical structure modification perspective.…”

“…Their conjugated diene counterparts (i.e., 1,3-dienes) are versatile and valuable chemical species that can be used as two-carbon or four-carbon synthons; 1,3-butadiene production is in the million metric tons every year and constantly increasing. 1 − 4 Although conjugated dienes feature a relatively simple and easily accessible structure, their chemical properties go far beyond those of simple olefins. While their reactivity has been extensively studied and it represents a rich area of research with continuous innovations, mainly using transition metal catalysis, competitive metal-free approaches are still lacking.…”

Nickel-Catalyzed Four-Component Carbonylation of 1,3-Butadiene To Access β,γ-Unsaturated Ketones

“…Moreover, these methods usually suffer from low regioselectivity for some materials. 1,3-Butadiene, the simplest conjugated diene in nature, is a low-cost and abundant carbon source produced from liquid cracking, and its unique molecular structure H 2 CCH–CHCH 2 offers a wide range of possibilities for chemical transformation . Therefore, 1,3-butadiene is an attractive surrogate to access the allyl substrates …”

Radical Crotylation of Aldehydes with 1,3-Butadiene by Photoredox Cobalt and Titanium Dual Catalysis

“…20,21 Recently, 1,3-butadiene has emerged as an attractive alternative allyl source for carbonyl allylation due to its potential for overall synthetic efficiency and environmental sustainability. 18,22 For instance, Krische and his colleagues devised a crotylation method for aldehydes using ruthenium and chiral phosphoric acid catalysis through the utilization of a "borrowing hydrogen" approach, which significantly shows perfect atom economy. 23−25 Buchwald and his team developed an elegant and highly effective asymmetric CuH-catalyzed reductive crotylation of ketones with butadiene that exhibited outstanding regio-and enantioselectivity control.…”

“…The most efficient method for synthesizing homoallylic alcohols is through the allylation reaction of carbonyls with nucleophilic allylmetal species. − However, this process often involves the production of air- and water-sensitive π-allylmetal reagents, which can be difficult to work with and require preactivated allylic halides . 1,3-Butadiene is a readily available industrial raw material produced from the C4 fraction of liquid cracking and commonly used in the synthesis of synthetic rubbers via radical polymerization. , Recently, 1,3-butadiene has emerged as an attractive alternative allyl source for carbonyl allylation due to its potential for overall synthetic efficiency and environmental sustainability. , For instance, Krische and his colleagues devised a crotylation method for aldehydes using ruthenium and chiral phosphoric acid catalysis through the utilization of a “borrowing hydrogen” approach, which significantly shows perfect atom economy. − Buchwald and his team developed an elegant and highly effective asymmetric CuH-catalyzed reductive crotylation of ketones with butadiene that exhibited outstanding regio- and enantioselectivity control. − More recently, Xia’s group reported a novel photoredox- and Ni-catalyzed reductive crotylation of aldehydes with butadiene, which displays branch selectivity . From a reaction mechanism perspective, the crucial step in the catalytic cycle involves the hydrometalation (2e – ) of butadiene with a metal hydride, which generates nucleophilic π-allylmetal species.…”