14212-46-5

Upstream product

• 2550-26-7 4-Phenyl-2-butanone 
• 100-42-5 styrene 
• 3262-89-3 triphenylboroxine 
• 29443-41-2 β-phenylethylidenehydrazine 
• 98-86-2 acetophenone 
• 1083-30-3 dihydrochalcone 
• 26138-28-3 phenylytterbium iodide 
• 122-57-6 1-Phenylbut-1-en-3-one 
• 19332-07-1 2,4-diphenyl-butan-2-ol 
• 16606-47-6 2,4-diphenylbut-1-ene 
• 122-78-1 phenylacetaldehyde 
• 72807-24-0 (1-Phenylethyl)triphenylphosphoniumiodid 
• 1226953-84-9 4-phenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxoborolan-2-yl)butan-2-ol 
• 1226953-82-7 4,4,5,5-tetramethyl-2-(4-phenyl-2-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)oxy)butan-2-yl)-1,3,2-dioxaborolane 

Relevant academic research and scientific papers

Visible-light-controlled homo- and copolymerization of styrenes by a bichromophoric Ir-Pd catalyst

Visible-light-controlled polymerization was achieved by a bichromophoric organopalladium catalyst which possesses a naphthyl-substituted cyclometallated Ir(iii) light-absorbing moiety. The complex was highly active toward styrene polymerization upon visible-light irradiation, and its photoactivity toward polymerization and dimerization was switchable. On the basis of the switching activity, controlled copolymerization of styrene and vinyl ether was achieved upon photo-irradiation to give the corresponding copolymers. This journal is

Olefin functionalization/isomerization enables stereoselective alkene synthesis

Despite tremendous efforts aimed at devising methods for stereoselective alkene synthesis, critical challenges are yet to be addressed. Direct access to a diverse range of 1-aryl(boryl)-1-methyl-functionalized tri- and tetrasubstituted trans alkenes, entities that are prevalent in many important molecules, through a catalytic manifold from readily available α-olefin substrates remains elusive. Here, we demonstrate that catalytic amounts of a non-precious N-heterocyclic carbene–Ni(I) complex in conjunction with a sterically bulky base promote site- and trans-selective union of monosubstituted olefins with a wide array of electrophilic reagents to deliver tri- and tetrasubstituted alkenes in up to 92% yield and >98% regio- and stereoselectivity. The protocol is amenable to the preparation of carbon- and heteroatom-substituted C=C bonds, providing distinct advantages over existing transformations. Utility is highlighted through concise stereoselective synthesis of biologically active compounds. [Figure not available: see fulltext.].

A donor-acceptor complex enables the synthesis of: E -olefins from alcohols, amines and carboxylic acids

Olefins are prevalent substrates and functionalities. The synthesis of olefins from readily available starting materials such as alcohols, amines and carboxylic acids is of great significance to address the sustainability concerns in organic synthesis. Metallaphotoredox-catalyzed defunctionalizations were reported to achieve such transformations under mild conditions. However, all these valuable strategies require a transition metal catalyst, a ligand or an expensive photocatalyst, with the challenges of controlling the region- and stereoselectivities remaining. Herein, we present a fundamentally distinct strategy enabled by electron donor-acceptor (EDA) complexes, for the selective synthesis of olefins from these simple and easily available starting materials. The conversions took place via photoactivation of the EDA complexes of the activated substrates with alkali salts, followed by hydrogen atom elimination from in situ generated alkyl radicals. This method is operationally simple and straightforward and free of photocatalysts and transition-metals, and shows high regio- and stereoselectivities.

Highly Stereoselective Positional Isomerization of Styrenes via Acid-Catalyzed Carbocation Mechanism

The first transition metal-free highly stereoselective positional isomerization of various α-alkyl styrenes through a carbocation mechanism triggered strategy is developed by using Al(OTf)3 as a hidden Br?nsted acid catalyst, which provides facile access to value-added acyclic tri- and tetra-substituted alkenes in good yields with high stereoselectivity under mild conditions. The practicality of this protocol is further highlighted by the gram-scale synthesis, high stereoselectivity, good functional group tolerance, and simple operation. Mechanistic studies support that Al(OTf)3 acts as a hidden Br?nsted acid catalyst and a carbocation intermediate is formed.

Cobalt(II)-Catalyzed Stereoselective Olefin Isomerization: Facile Access to Acyclic Trisubstituted Alkenes

Stereoselective synthesis of trisubstituted alkenes is a long-standing challenge in organic chemistry, due to the small energy differences between E and Z isomers of trisubstituted alkenes (compared with 1,2-disubstituted alkenes). Transition metal-catalyzed isomerization of 1,1-disubstituted alkenes can serve as an alternative approach to trisubstituted alkenes, but it remains underdeveloped owing to issues relating to reaction efficiency and stereoselectivity. Here we show that a novel cobalt catalyst can overcome these challenges to provide an efficient and stereoselective access to a broad range of trisubstituted alkenes. This protocol is compatible with both mono- and dienes and exhibits a good functional group tolerance and scalability. Moreover, it has proven to be a useful tool to construct organic luminophores and a deuterated trisubstituted alkene. A preliminary study of the mechanism suggests that a cobalt-hydride pathway is involved in the reaction. The high stereoselectivity of the reaction is attributed to both a π-πstacking effect and the steric hindrance between substrate and catalyst.

Synthesis of Tetrahydroisoindolinones via a Metal-Free Dehydrogenative Diels-Alder Reaction

A metal-free dehydrogenative Diels-Alder reaction of substituted alkenes for the synthesis of tetrahydroisoindolinones has been exploited for the first time. This new method features functional group tolerance and broad substrate scope, providing an efficient access to biologically active tetrahydroisoindolinone skeletons with endo steroselectivity in good to excellent yields. (Figure presented.).

Nickel-Catalyzed Direct Synthesis of Aryl Olefins from Ketones and Organoboron Reagents under Neutral Conditions

Nickel-catalyzed addition of arylboron reagents to ketones results in aryl olefins directly. The neutral condition allows acidic protons of alcohols, phenols, and malonates to be present, and fragile structures are also tolerated.

Ruthenium(II)-catalyzed olefination: Via carbonyl reductive cross-coupling

Natural availability of carbonyl groups offers reductive carbonyl coupling tremendous synthetic potential for efficient olefin synthesis, yet the catalytic carbonyl cross-coupling remains largely elusive. We report herein such a reaction, mediated by hydrazine under ruthenium(ii) catalysis. This method enables facile and selective cross-couplings of two unsymmetrical carbonyl compounds in either an intermolecular or intramolecular fashion. Moreover, this chemistry accommodates a variety of substrates, proceeds under mild reaction conditions with good functional group tolerance, and generates stoichiometric benign byproducts. Importantly, the coexistence of KOtBu and bidentate phosphine dmpe is vital to this transformation.

Stereoselective formation of trisubstituted vinyl boronate esters by the acid-mediated elimination of α-hydroxyboronate esters

The copper-catalyzed diboration of ketones followed by an acid-catalyzed elimination leads to the formation of 1,1-disubstituted and trisubstituted vinyl boronate esters with moderate to good yields and selectivity. Addition of tosic acid to the crude diboration products provides the corresponding vinyl boronate esters upon elimination. The trisubstituted vinyl boronate esters are formed as the (Z)-olefin isomer, which was established by subjecting the products to a Suzuki-Miyaura coupling reaction to obtain alkenes of known geometry.

Copper-catalyzed oxidative heck reactions between alkyltrifluoroborates and vinyl arenes

We report herein that potassium alkyltrifluoroborates can be utilized in oxidative Heck-type reactions with vinyl arenes. The reaction is catalyzed by a Cu(OTf)2/1,10-phenanthroline with MnO2 as the stoichiometric oxidant. In addition to the alkyl Heck, amination, esterification, and dimerization reactions of alkyltrifluoroborates are demonstrated under analogous reaction conditions. Evidence for an alkyl radical intermediate is presented.