34662-94-7

Upstream product

• 100-42-5 styrene 
• 2052-07-5 2-Bromobiphenyl 
• 86-00-0 2-nitrobiphenyl 
• 98-80-6 phenylboronic acid 
• 741695-45-4 (E)-2-styrylphenyl N,N-diethyl-O-carbamate 
• 122-78-1 phenylacetaldehyde 
• 1657-52-9 (E)-2-chlorostilbene 
• 100-52-7 benzaldehyde 
• 68622-84-4 (Z)-2-styryl-1,1'-biphenyl 
• 95-15-8 Benzo[b]thiophene 
• 854243-57-5 2-phenyl-bibenzyl-α-ol 
• 24388-23-6 2-phenyl-4,4,5,5-tetramethyl-1,3,2-dioxoborole 
• 153140-75-1 1-bromo-2-[(Z)-2-bromoethenyl]benzene 
• 1587-22-0 2-vinylbiphenyl 

Downstream Products

• 844-20-2 9-phenylphenanthrene 
• 68622-84-4 (Z)-2-styryl-1,1'-biphenyl 
• 10271-65-5 2-(phenylethynyl)-1,1'-biphenyl 
• 85-01-8 phenanthrene 
• 215-58-7 dibenzo[a,c]anthracene 
• 1572-46-9 9-benzylfluorene 
• 5235-80-3 9,10-dihydro-9-phenylphenanthrane 
• 205529-10-8 ((E)-2-Biphenyl-2-yl-1-phenyl-vinyl)-diphenyl-phosphane 
• 205529-12-0 ((Z)-2-Biphenyl-2-yl-1-phenyl-vinyl)-diphenyl-phosphane 
• 264912-30-3 1-(o-biphenylyl)-1,2-dibromo-2-phenylethane 
• 4325-76-2 1-phenyl phenanthrene 

Relevant academic research and scientific papers

Palladium-Catalyzed Mizoroki-Heck Reaction of Nitroarenes and Styrene Derivatives

We have developed a Mizoroki-Heck reaction of nitroarenes with alkenes under palladium catalysis. The use of a Pd/BrettPhos catalyst promoted the alkenylation, whereas other catalysts led to a decrease in the product yield. In addition to nitroarenes, nitroheteroarenes were also applicable to the present reaction. The combination of a nucleophilic aromatic substitution (SNAr) with the denitrative alkenylation produced a multifunctionalized arene in a one-pot operation.

2,3-Dichloro-5,6-dicyano-para-benzoquinone (DDQ)/methanesulfonic acid (MsOH)-mediated intramolecular arene-alkene oxidative coupling

An efficient intramolecular arene-alkene oxidative coupling of 1,4-diaryl-1,3-butadienes has been developed involving the use of a 2,3-dichloro-5,6-dicyano-para-benzoquinone (DDQ)/acid catalyst. The reaction involves the generation of a radical cation by abstraction of an electron from the substrate with DDQ, an intramolecular Friedel-Crafts-type reaction, and the loss of hydrogen radical.

Straightforward synthesis of phenanthrenes from styrenes and arenes

Semi-one-pot synthesis of phenanthrenes from styrenes and arenes was developed through cross-dehydrogenative coupling. A sequence of Heck-type coupling and photo-cyclization were involved and a variety of functionalities were tolerated. This method provides an effective and practical protocol towards the synthesis of substituted phenanthrenes. The Royal Society of Chemistry 2012.

Palladium-catalyzed annulation of 1,2-diborylalkenes and -arenes with 1-bromo-2-[(Z)-2-bromoethenyl]arenes: A modular approach to multisubstituted naphthalenes and fused phenanthrenes

(Z)-1,2-Diaryl-1,2-bis(pinacolatoboryl)ethenes underwent double-cross-coupling reactions with 1-bromo-2-[(Z)-2-bromoethenyl]arenes in the presence of [Pd(PPh3)4] as a catalyst and 3 M aqueous Cs2CO3 as a base in THF at 80 °C. The double-coupling reaction gave multisubstituted naphthalenes in good to high yields. Annulation of 1,2-bis(pinacolatoboryl)arenes with bromo(bromoethenyl)arenes in the presence of a catalyst system that consisted of [Pd2(dba)3] (dba=dibenzylideneacetone) and 2-dicyclohexylphosphino-2′,6′- dimethoxybiphenyl (SPhos) under the same conditions produced fused phenanthrenes in good to high yields. The first annulation coupling occurred regiospecifically at the bromoethenyl moiety. This procedure is applicable to the facile synthesis of polysubstituted anthracenes, benzothiophenes, and dibenzoanthracenes through a double annulation pathway by using the corresponding dibromobis[(Z)-2-bromoethenyl]benzenes as diboryl coupling partners. Copyright

Suzuki-Miyaura cross-coupling of aryl carbamates and sulfamates: Experimental and computational studies

The first Suzuki-Miyaura cross-coupling reactions of the synthetically versatile aryl O-carbamate and O-sulfamate groups are described. The transformations utilize the inexpensive, bench-stable catalyst NiCl 2(PCy3)2 to furnish biaryls in good to excellent yields. A broad scope for this methodology has been demonstrated. Substrates with electron-donating and electron-withdrawing groups are tolerated, in addition to those that possess ortho substituents. Furthermore, heteroaryl substrates may be employed as coupling partners. A computational study providing the full catalytic cycles for these cross-coupling reactions is described. The oxidative addition with carbamates or sulfamates occurs via a five-centered transition state, resulting in the exclusive cleavage of the aryl C-O bond. Water is found to stabilize the Ni-carbamate catalyst resting state, which thus provides rationalization of the relative decreased rate of coupling of carbamates. Several synthetic applications are presented to showcase the utility of the methodology in the synthesis of polysubstituted aromatic compounds of natural product and bioactive molecule interest.

N,N-diethyl O-carbamate: Directed metalation group and orthogonal Suzuki-Miyaura cross-coupling partner

(Chemical Equation Presented) The first Suzuki-Miyaura cross-coupling of an aryl O-carbamate, a versatile and powerful directed metalation group (DMG) in directed ortho metalation (DoM) chemistry, is described using the inexpensive, bench-stable catalyst NiCl2(PCy3)2. Broad synthetic scope and good efficiency are demonstrated for aryl and heteroaryl O-carbamates. The role of water and hydrolysis equilibrium between free boronic acid and boroxine was established to be a crucial parameter for this transformation. When combined with DoM and traditional Pd-catalyzed Suzuki-Miyaura strategies, the methodology offers concise routes to uniquely substituted molecules, avoiding the need for protection/deprotection of the phenol and the use of strongly nucleophilic cross-coupling partners.

Manganese-catalyzed substitution of activated aryl halides (X = Cl, Br and F) and aryl ethers by organomagnesium reagents

In the presence of manganese chloride (10%), Grignard reagents readily react in THF with aryl bromides, chlorides and even fluorides, as well as aryl methyl ethers bearing in the ortho- or para-position an electron withdrawing activating group (CN, CH=NR, oxazoline). Aryl and N- or S- alkylmagnesium halides have been used successfully. The reaction is performed under mild conditions (0 °C to room temperature, 30 minutes to 24 hours) and leads to cross-coupling products in good yields.

Stereoselective addition of diphenylphosphine to substituted diphenylethynes: Synthetic, NMR and X-ray crystallographic studies

The base-catalysed addition of diphenylphosphine to the substituted diphenylethynes RC≡CR′ (R = Ph, R′ = Ph, o-tolyl, m-tolyl or 2-biphenyl; R = m-tolyl, R′ = o-tolyl or m-tolyl) yielded Ph2PC(R)=CHR′ and/or Ph2PCH(R)CH(R′)PPh2. Proton, 13C, 13P and two-dimensional rotating frame Overhauser enhancement 1H NMR spectra have been used to determine the stereochemical pathways of the reactions and the stereochemistry of the products. In general the more hindered alkynes undergo monoaddition ultimately to yield phosphinoalkenes with the Ph2P attached to the carbon bearing the least bulky substituent and cis to the olefinic proton, while for the less hindered alkynes the trans isomer is formed initially and this then reacts further to give mesolerythro-diphosphinoalkanes. Bis(o-tolyl)ethyne does not react with Ph2PH under the same conditions. Crystal structures were determined for E- and Z-Ph2P(Ph)C=CHPh and show distortions of interbond angles consistent with the pattern of strain implied by the foregoing reactions. The sulfides of the phosphinoalkenes and the Mo(CO)4 complexes of the diphosphinoalkanes were also prepared and their 1H, 13C and 31P NMR spectra recorded. In several cases the pattern of 13CO NMR signals for the complexes was used unambiguously to determine the stereochemistry of the parent diphosphines.

Photocyclization of 2-Vinylbiphenyls and Related Compounds under Triplet Sensitization: An Adiabatic Reaction on the Triplet Surface

The mechanism of the cyclization of 2-vinylbiphenyl derivatives under sensitization by the triplet state of xanthone has been studied by laser-flash photolysis.The first step of the mechanism is an adiabatic reaction giving a cyclized polyene in the tripl