68684-64-0

Upstream product

• 622-76-4 1-phenyl-1-butyne 
• 88284-48-4 2-(trimethylsilyl)phenyl trifluoromethanesulfonate 
• 591-51-5 phenyllithium 
• 13029-09-9 2,2'-dibromobiphenyl 
• 179117-39-6 (Z)-2,2'-(1-phenylbut-1-ene-1,2-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) 
• 947-84-2 2-Biphenylcarboxylic acid 
• 189999-35-7 [1,1'-biphenyl]-2,2'-iodonium trifluoromethanesulfonate 
• 412323-64-9 1-biphenyl-2-yl-2-phenoxy-1-phenyl-butan-1-ol 
• 64-19-7 acetic acid 
• 4433-14-1 2,2-diethyl-3-biphenyl-2-yl-3-phenyl-oxirane 
• 10035-10-6 hydrogen bromide 

Relevant academic research and scientific papers

Palladium catalyzed co-trimerization of benzyne with alkynes. A facile method for the synthesis of phenanthrene derivatives

A facile method for the synthesis of phenanthrene derivatives by the palladium catalyzed co-trimerization of benzyne with alkynes is described.

Base-catalyzed diborylation of alkynes: synthesis and applications of cis-1,2-bis(boryl)alkenes

An efficient, transition-metal free, and practical approach to cis-bis(boryl)alkenes from various alkynes was disclosed in the presence of a catalytic amount of K2CO3 under mild conditions. Meanwhile, tetrasubstituted alkenes and phenanthrene derivatives were readily constructed from the target diborylalkenes via Suzuki-Miyaura cross coupling.

Pd catalyzed insertion of alkynes into cyclic diaryliodoniums: A direct access to multi-substituted phenanthrenes

Cyclic diaryliodoniums remain unexplored compared to linear iodoniums. In our current work, internal alkynes were for the first time applied to react with cyclic iodoniums, catalyzed by Pd, resulting in a [4 + 2] benzannulation. Our work offers a new strategy to synthesize multi-substituted phenanthrene derivatives which are not easily accessed by conventional methods.

Palladium-catalyzed double cross-coupling reaction of 1,2- bis(pinacolatoboryl)alkenes and -arenes with 2,2′-dibromobiaryls: Annulative approach to functionalized polycyclic aromatic hydrocarbons

This study demonstrates that the double cross-coupling reaction of 1,2-bis(pinacolatoboryl)alkenes and -arenes with 2,2′-dibromobiaryls proceeds smoothly with the aid of a catalytic amount of Pd(PPh3) 4 in the presence of excess base to give a variety of polycyclic aromatic hydrocarbons, such as phenanthrenes, [5]helicene, dithienobenzenes, triphenylenes, dibenzo[g,p]chrysenes, and triphenyleno[1,2-b:4,3-b′] dithiophenes in good to high yields. It is noteworthy that the annulations using 2,2′-dibromooctafluorobiphenyl as an electrophile furnish the otherwise difficult to synthesize octafluorophenanthrenes and semi-fluorinated dibenzo[g,p]chrysenes in high yields.

Palladium-catalyzed intermolecular decarboxylative coupling of 2-phenylbenzoic acids with alkynes via C-H and C-C bond activation

A novel protocol for palladium-catalyzed intermolecular formal [4 + 2] annulation of 2-phenylbenzoic acids with alkynes is described. Acridine is shown to be essential for the high reaction efficiency. Phenanthrene derivatives are formed in moderate to good yields without coupling (pseudo)halides or organometallic species.

Palladium-catalyzed annulation of vic-bis(pinacolatoboryl)alkenes and -phenanthrenes with 2,2′-dibromobiaryls: Facile synthesis of functionalized phenanthrenes and dibenzo[g,p]chrysenes

(Chemical Equation Presented) Double-cross: An annulation approach to functionalized polycyclic aromatic hydrocarbons involving a palladium-catalyzed double cross-coupling reaction of vic-diborylalkenes and -phenanthrenes with 2,2′-dibromobiaryls led to a variety of phenanthrenes and dibenzo-[g,p]chrysenes, as well as [5]helicenes, dithienobenzenes, and triphenyleno[1,2-b:4,3-b′]dithiophenes (see scheme; Bpin = pinacolatoboryl).

Generation of benzocyclobutadiene derivatives from zirconaindene derivatives

Zirconaindene derivatives produced benzocyclobutadiene derivatives in situ in the presence of CuCl and 1,4-naphthoquinone, which afforded their dimers, 6a, 10b-dihydrobenzo[a]biphenylenes and dibenzosemibullvalenes or dibenzo[a,e]-cycloctenes.

Palladium-catalyzed controlled carbopalladation of benzyne

2-Trimethylsilylphenyl trifluoromethanesulfonate 1a, a benzyne precursor, reacted with the allylic chlorides 2a - f in the presence of CsF (2.0 equiv) and Pd2(dba)3·CHCl3 (2.5 mol %)-dppf (5 mol %) in a 1:1 mixed solvent of CH3CN and THF to produce the phenanthrene derivatives 3 along with their minor regioisomers 4 in good yields (i) and the reaction of 1a with 2a and the internal alkynes 15a,c - e afforded the naphthalene derivatives 16 in moderate yields (ii). The reaction of benzyne precursor 1a with the alkynes 15a - c,f - h in the presence of Pd(OAc)2 (5 mol %)-(o-tolyl)3P (5 mol %) catalyst and CsF (2.0 equiv) in CH3CN gave the phenanthrene derivatives 17 (iii), whereas the reaction of 1a with the alkynes 15a,b,i in the presence of the same catalysts and CsF in CH3CN - toluene gave the indene derivatives 18 in good yields (iv). Detailed mechanistic investigation revealed that the former two reactions i and ii proceed through carbopalladation to free benzyne, while the latter two reactions iii and iv proceed through the nonfree benzyne mechanism, in which the initial step of the catalytic cycle begins with Pd(0) insertion to the Ar - OTf bond of 1.