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Upstream product

• 943-27-1 4'-t-butylacetophenone 
• 253185-03-4 tert-butylbenzene 
• 101325-12-6 1-(4-tert-butylphenyl)ethanol 
• 772-38-3 4-tert-Butylphenylacetylene 
• 33458-07-0 1-(4-tert.-Butylphenyl)-1.2-dibromaethan 
• 1746-23-2 4-tert-Butylstyrene 

Downstream Products

• 1621387-23-2 C₁₂H₁₇BO₂ 
• 1621387-08-3 2-((1-(4-(tert-butyl)phenyl)vinyl)oxy)isoindoline-1,3-dione 
• 92975-15-0 2,3-di(tert-butylphenyl)-1,3-butadiene 
• 1579298-22-8 (S)-2-(4-(tert-butyl)phenyl)-2-(chloromethyl)cyclopentanone 
• 1579298-04-6 1-(1-(4-(tert-butyl)phenyl)vinyl)cyclobutanol 

Relevant academic research and scientific papers

Rhodium(III)-Catalyzed Cyclopropanation of Unactivated Olefins Initiated by C-H Activation

We have developed a rhodium(III)-catalyzed cyclopropanation of unactivated olefins initiated by an alkenyl C-H activation. A variety of 1,1-disubstituted olefins undergo efficient cyclopropanation with a slight excess of alkene stoichiometry. A series of mechanistic interrogations implicate a metal carbene as an intermediate.

Catalytic Asymmetric Halogenation/Semipinacol Rearrangement of 3-Hydroxyl-3-vinyl Oxindoles: A Stereodivergent Kinetic Resolution Process

A highly enantioselective halogenation/semipinacol rearrangement of isatin-derived allylic alcohols has been developed with a chiral N,N′-dioxide/ScIII complex as catalyst. This strategy involved a pivotal stereodivergent kinetic resolution process and provided a facile and efficient entry to optically active halo-substituted quinolone derivatives and quinoline alkaloids with a quaternary stereocenter simultaneously under mild reaction conditions. Based on the control experiments together with kinetic studies and DFT calculations, a possible catalytic cycle was proposed to illustrate the reaction process and enantiocontrol.

Rh(III)-Catalyzed C-H Activation-Initiated Directed Cyclopropanation of Allylic Alcohols

We have developed a Rh(III)-catalyzed diastereoselective [2+1] annulation onto allylic alcohols initiated by alkenyl C-H activation of N-enoxyphthalimides to furnish substituted cyclopropyl-ketones. Notably, the traceless oxyphthalimide handle serves three functions: directing C-H activation, oxidation of Rh(III), and, collectively with the allylic alcohol, in directing cyclopropanation to control diastereoselectivity. Allylic alcohols are shown to be highly reactive olefin coupling partners leading to a directed diastereoselective cyclopropanation reaction, providing products not accessible by other routes.

Rh(III)-Catalyzed C-H Activation-Initiated Directed Cyclopropanation of Allylic Alcohols

We have developed a Rh(III)-catalyzed diastereoselective [2+1] annulation onto allylic alcohols initiated by alkenyl C-H activation of N-enoxyphthalimides to furnish substituted cyclopropyl-ketones. Notably, the traceless oxyphthalimide handle serves three functions: Directing C-H activation, oxidation of Rh(III), and, collectively with the allylic alcohol, in directing cyclopropanation to control diastereoselectivity. Allylic alcohols are shown to be highly reactive olefin coupling partners leading to a directed diastereoselective cyclopropanation reaction, providing products not accessible by other routes.

Intermolecular Carboamination of Unactivated Alkenes

Herein, we report the first example of group transfer radical addition of O-vinylhydroxylamine derivatives onto unactivated alkenes. By utilizing O-vinylhydroxylamine derivatives as both the N- and C-donors, this reaction enables intermolecular carboamination of unactivated alkenes in an atom economical fashion. As the process is initiated through N-radical addition followed by C-transfer, linear carboamination products are afforded. This differs from canonical radical carbofunctionalization of olefins, which typically favors branched product owing to initiation by C-radical addition.

Cyclic Hypervalent Iodine Reagents for Azidation: Safer Reagents and Photoredox-Catalyzed Ring Expansion

Azides are building blocks of increasing importance in synthetic chemistry, chemical biology, and materials science. Azidobenziodoxolone (ABX, Zhdankin reagent) is a valuable azide source, but its safety profile has not been thoroughly established. Herein, we report a safety study of ABX, which shows its hazardous nature. We introduce two derivatives, tBu-ABX and ABZ (azidobenziodazolone), with a better safety profile, and use them in established photoredox- and metal-mediated azidations, and in a new ring-expansion of silylated cyclobutanols to give azidated cyclopentanones.

Regio-specific polyacetylenes synthesized from anionic polymerizations of template monomers

Substituted polyacetylenes with alkylphenyl side groups and head-to-head regioregularity were prepared through anionic living polymerization of template monomers and subsequent dehydrogenation process. The template monomers have the structure of 2, 3-disubstituted-1, 3-butadienes prepared by palladium-catalyzed Kumada coupling of the corresponding vinyl bromides. Anionic polymerizations of the template monomers produced narrow disperse substituted polybutadiene precursors with exclusive 1, 4-enchainment. The precursors were converted into soluble polyacetylene derivatives via two methods, e.g., bromination followed by elimination of HBr, and direct dehydrogenation by 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone (DDQ), both resulting in dark colored products with significant red shift in UV spectra. The obtained head-to-head polyacetylene derivatives exhibited highly thermal stability, possibly due to trans-rich and/or head-to-head chain configurations. The microstructures of the poly(2, 3-dialkylphenyl butadiene) precursors were analyzed in detail using NMR spectroscopy with regard to the solvent effect during polymerization. Block copolymers containing substituted polyacetylene segments were prepared through sequential anionic polymerization of different monomers, followed by dehydrogenation transformation. The present synthesis may serve as a new strategy for tailoring molecular structures of polyacetylene-based polymers by virtue of anionic living polymerization techniques.

Metal-free regioselective hydrobromination of alkynes through CH/CBr activation

A metal-free regioselective hydrobromination of alkynes has been developed to provide the Markovnikov-type vinyl bromides in good yields using dibromomethane/N,N-dimethylaniline as in-situ 'HBr' source. This protocol also represents an elegant example of the activation of sp2 CH and CBr bonds in one pot, in which 'HBr' is generated and transferred under mild metal-free conditions. D-incorporated experiments were employed to investigate the reaction mechanism and a plausible reaction path was proposed.

Rh(III)-catalyzed cyclopropanation initiated by C-H activation: Ligand development enables a diastereoselective [2 + 1] annulation of N-enoxyphthalimides and alkenes

N-Enoxyphthalimides undergo a Rh(III)-catalyzed C-H activation initiated cyclopropanation of electron deficient alkenes. The reaction is proposed to proceed via a directed activation of the olefinic C-H bond followed by two migratory insertions, first across the electron-deficient alkene and then by cyclization back onto the enol moiety. A newly designed isopropylcyclopentadienyl ligand drastically improves yield and diastereoselectivity.

The concerted addition of HBr to aryl alkynes; orthogonal pi bond selectivity

In a weakly acidic solution, the addition of HBr to 1-phenylprop-1-yne produces predominantly the anti-Markovnikov product. In this paper, we consider five possible explanations for this behavior and conclude that the concerted addition is occurring on the acetylenic π bond orthogonal to the extended aromatic π system. The electronic effect of the distal methyl group and the steric hindrance of the coplanar phenyl ring combine to promote bromide attack at the β carbon. Attack on this π bond is insensitive to the electronic effect of meta and para substituents on the ring but is very (sterically) sensitive toward all ortho substituents.