1138077-60-7

Upstream product

• 405-99-2 para-fluorostyrene 
• 25015-63-8 4,4,5,5-tetramethyl-[1,3,2]-dioxaboralane 
• 75230-49-8 N′-(1-(4-fluorophenyl)ethylidene)-4-methylbenzenesulfonohydrazide 
• 403-42-9 1-(4-fluorophenyl)ethanone 
• 766-98-3 1-ethynyl-4-fluorobenzene 
• 850567-55-4 2-(1-(4-fluorophenyl)vinyl)-4,4,5,5-tetramethyl-1,3-dioxa-2-borolane 
• 73183-34-3 bis(pinacol)diborane 
• 403-40-7 1-(4-fluorophenyl)ethylamine 
• 450-58-8 2-naphthyldiazonium tetrafluoroborate 
• 459-57-4 4-fluorobenzaldehyde 
• 917-54-4 methyllithium 
• 352-34-1 4-fluoro-1-iodobenzene 

Downstream Products

• 403-42-9 1-(4-fluorophenyl)ethanone 
• 403-41-8 (S)-1-(4-fluorophenyl)ethan-1-ol 
• 403-41-8 (R)-1-(4-fluorophenyl)ethan-1-ol 

Relevant academic research and scientific papers

Pd-Catalyzed Regioselective Arylboration of Vinylarenes

A palladium-catalyzed 1,2-arylboration of vinylarenes with aryldiazonium tetrafluoroborates and bis(pinacolato)diboron has been disclosed. It is reported for the first time that styrene derivatives can be successfully employed as good substrates for 1,2-arylboration of alkenes. Mechanistic studies suggest that no Pd-H reinsertion occurred under our standard conditions, which is the key for the success of this transformation.

Markovnikov-Selective Hydroboration of Olefins Catalyzed by a Copper N-Heterocyclic Carbene Complex

The efficient and atom-economical hydroboration of alkenes and alkynes using an N-heterocyclic carbene (NHC) copper hydroxide catalyst has been developed. An equimolar combination of substrate and HBpin allows for the selective Markovnikov hydroboration of alkenes and alkynes. A variety of functional groups were tolerated in good to excellent yield. This system features a facile reaction setup, atom economy, high selectivity, and an easily synthesized copper-NHC catalyst.

Photoswitching of Copper(I) Chromophores with Dithienylethene-Based Ligands

Metal-containing dithienylethenes offer new opportunities for variations in photochromic behavior. This work reports a series of copper(I) complexes containing dithienylethene-based bidentate phosphine ligands displaying varying photochromic properties. A copper dimer is used as a common precursor, allowing diverse photochromic functionality to be achieved. Calculations show that ring closing of the peripheral dithienyl moiety leads to a slight expansion of the five-membered metallacycle. The photochromic properties and photoreaction quantum yields of these complexes are tunable by variation of the ancillary ligands. Photoswitchable catalysis of a hydroboration reaction with one of the copper complexes is demonstrated.

Rhodium-Catalyzed Regiodivergent Synthesis of Alkylboronates via Deoxygenative Hydroboration of Aryl Ketones: Mechanism and Origin of Selectivities

Here, we report an efficient rhodium-catalyzed deoxygenative borylation of ketones to synthesize alkylboronates, in which the regioselectivity can be switched by the choice of the ligand. The linear alkylboronates were obtained exclusively in the presence of P(nBu)3, and PPh2Me favored the formation of branched alkylboronates. The protocol also allows access to 1,1,2-triboronates from the readily available ketones. Mechanistic studies suggest that this Rh-catalyzed deoxygenative borylation of ketones goes through an alkene intermediate, which undergoes regiodivergent hydroboration to afford linear and branched alkylboronates. The different steric effects of PPh2Me and P(nBu)3 were found to be responsible for product selectivity by density functional theory calculations. The alkene intermediate can alternatively undergo sequential dehydrogenative borylation and hydroboration to deliver the triboronates.

Chemoselective Cross-Coupling of gem-Borazirconocene Alkanes with Aryl Halides

The direct and chemoselective conversion of the carbon-metal bond of gem-dimetallic reagents enables rapid and sequential formation of multiple carbon-carbon and carbon-heteroatom bonds, thus representing a powerful method for efficiently increasing structural complexity. Herein, we report a visible-light-induced, nickel-catalyzed, chemoselective cross-coupling reaction between gem-borazirconocene alkanes and diverse aryl halides, affording a wide range of alkyl Bpin derivatives in high yields with excellent regioselectivity. This practical method features attractively simple reaction conditions and a broad substrate scope. Additionally, we systematically investigated a Bpin-directed chain walking process underlying the regioselectivity of alkylzirconocenes, thus uncovering the mechanism of the remote functionalization of internal olefins achieved with our method. Finally, DFT calculations indicate that the high regioselectivity of this reaction originates from the directing effect of the Bpin group.

Erratum: Markovnikov-selective hydroboration of olefins catalyzed by a copper N-heterocyclic carbene complex (Organometallics (2019) 38:17 (3322-3326) DOI: 10.1021/acs.organomet.9b00394)

It has come to our attention that some of the products listed in Table 2 of the article and in eq 1 have the incorrect stereochemistry. The reactions of alkynes with HBpin give the linear E-olefin products, not the branched products as were shown. 1H NMR spectra clearly show two doublets with a large J (18 Hz) for the trans-hydrogens of the alkene product. A DEPT-135 spectrum also confirms that CH and not CH2 is present. Corrected eq 1, Table 2, TOC graphic are shown. Note that the alkene addition products are correctly assigned as branched, displaying a doublet and a quartet for the methyl and methane groups, respectively. NMR spectra for all products are included in the revised Supporting Information. We thank Prof. Jaesook Yun for pointing out this error, as her group has worked on related copper borylations for many years.

A phenalenyl-based nickel catalyst for the hydroboration of olefins under ambient conditions

In this report, nickel-catalyzed hydroboration of vinylarenes and aliphatic alkenes is investigated. The non-innocent phenalenyl ligand moiety in the nickel complex Ni(PLY)2(THF)2 (1) was utilized as an electron reservoir for the sel

Hydroboration of terminal olefins with pinacolborane catalyzed by new 2-iminopyrrolyl iron(ii) complexes

Four paramagnetic 14-electron tetracoordinated Fe(ii) complexes of 5-substituted-2-iminopyrrolyl ligands of the type [Fe{κ2N,N′-5-R-NC4H2-2-C(H)N(2,6-iPr2-C6H3)}(Py)Cl], with R = 2,6-Me2-C6H3 (1a), 2,4,6-iPr3-C6H2 (1b), 2,4,6-Ph3-C6H3 (1c) and CPh3 (1d), were synthesized in moderate yields by reacting the respective 5-substituted-2-iminopyrrolyl potassium salts KLa-d with FeCl2(Py)4 in toluene. Complexes 1a-d were characterized by 1H NMR, FTIR spectroscopies, elemental analysis and by the Evans method, the corresponding effective magnetic moments showing a high-spin electronic nature. X-ray diffraction studies on complexes 1a and 1c showed distorted tetrahedral coordination geometries. Complexes 1a-c, activated with K(HBEt3), were efficient catalyst systems for the hydroboration of several terminal alkenes with pinacolborane in good to high yields (50-90%). This system mainly yielded the respective anti-Markovnikov addition products, except when styrenes were used. A screening of the hydroboration of styrene catalyzed by complexes 1a-c activated with K(HBEt3) showed that the selectivity in the Markovnikov product increased with increasing steric bulkiness of the R group, exhibiting selectivities up to 91%. Additionally, the stoichiometric reaction of complex 1b with K(HBEt3) over 30 minutes yielded the mixture of hydride species 2 and 22 (mixture I). On the other hand, when reacting the same components over 16 h, the Fe(i) complex 3 was also identified in the mixture, in addition to 2 + 22 (mixture II). These mixtures were characterized in solution by the Evans method and in the solid state by elemental analysis, 57Fe M?ssbauer and FTIR spectroscopies, compounds 22 and 3 being also analyzed by X-ray diffraction. These results suggest that the corresponding catalytic cycle follows the borane oxidative addition route to a Fe(i) species.

Manganese-Catalyzed Hydrofunctionalization of Alkenes

The manganese-catalyzed hydrosilylation and hydroboration of alkenes has been developed using a single manganese(II) precatalyst and reaction protocol. Both reactions proceed with excellent control of regioselectivity and in high yields across a variety of sterically and electronically differentiated substrates (25 examples). Alkoxide activation, using NaOtBu, was key to precatalyst activation and reactivity. Catalysis was achieved across various functional groups and on gram-scale for both the developed methodologies with catalysts loadings as low as 0.5 mol %.

Cobalt-Catalyzed Hydroboration of Alkenes, Aldehydes, and Ketones

An operationally convenient and general method for hydroboration of alkenes, aldehydes, and ketones employing Co(acac)3 as a precatalyst is reported. The hydroboration of alkenes in the presence of HBpin, PPh3, and NaOtBu affords good to excellent yields with high Markovnikov selectivity with up to 97:3 branched/linear selectivity. Moreover, Co(acac)3 could be used effectively to hydroborate aldehydes and ketones in the absence of additives under mild reaction conditions. Inter- and intramolecular chemoselective reduction of the aldehyde group took place over the ketone functional group.