634152-97-9

Upstream product

• 36282-40-3 (3-methoxyphenyl)magnesium bromide 
• 6630-33-7 ortho-bromobenzaldehyde 
• 2398-37-0 3-methoxyphenyl bromide 
• 10365-98-7 3-methoxyphenylboronic acid 

Downstream Products

• 890098-06-3 (2-bromophenyl)(3-methoxyphenyl)methanone 
• 2523-46-8 2-methoxy-9H-fluorene 
• 26060-13-9 4-methoxy-9H-fluorene 
• 1183669-56-8 1-(2-bromophenyl)-1-(3-methoxyphenyl)ethanol 
• 1569315-57-6 6-(3-methoxyphenyl)-6-methyl-6H-benzo[c]chromene 
• 98-86-2 acetophenone 
• 634152-98-0 1-bromo-2-(3-methoxybenzyl)benzene 

Relevant academic research and scientific papers

Au-catalyzed biaryl coupling to generate 5- to 9-membered rings: Turnover-limiting reductive elimination versus π-complexation

The intramolecular gold-catalyzed arylation of arenes by aryl-trimethylsilanes has been investigated from both mechanistic and preparative aspects. The reaction generates 5- to 9-membered rings, and of the 44 examples studied, 10 include a heteroatom (N, O). Tethering of the arene to the arylsilane provides not only a tool to probe the impact of the conformational flexibility of Ar-Au-Ar intermediates, via systematic modulation of the length of aryl-aryl linkage, but also the ability to arylate neutral and electron-poor arenes-substrates that do not react at all in the intermolecular process. Rendering the arylation intramolecular also results in phenomenologically simpler reaction kinetics, and overall these features have facilitated a detailed study of linear free energy relationships, kinetic isotope effects, and the first quantitative experimental data on the effects of aryl electron demand and conformational freedom on the rate of reductive elimination from diaryl-gold(III) species. The turnover-limiting step for the formation of a series of fluorene derivatives is sensitive to the reactivity of the arene and changes from reductive elimination to π-complexation for arenes bearing strongly electron-withdrawing substituents (σ > 0.43). Reductive elimination is accelerated by electron-donating substituents (ρ = -2.0) on one or both rings, with the individual σ-values being additive in nature. Longer and more flexible tethers between the two aryl rings result in faster reductive elimination from Ar-Au(X)-Ar and lead to the π-complexation of the arene by Ar-AuX2 becoming the turnover-limiting step.

Au-Catalyzed Biaryl Coupling to Generate 5- To 9-Membered Rings: Turnover-Limiting Reductive Elimination versus ?-Complexation

The intramolecular gold-catalyzed arylation of arenes by aryl-trimethylsilanes has been investigated from both mechanistic and preparative aspects. The reaction generates 5- to 9-membered rings, and of the 44 examples studied, 10 include a heteroatom (N, O). Tethering of the arene to the arylsilane provides not only a tool to probe the impact of the conformational flexibility of Ar-Au-Ar intermediates, via systematic modulation of the length of aryl-aryl linkage, but also the ability to arylate neutral and electron-poor arenes - substrates that do not react at all in the intermolecular process. Rendering the arylation intramolecular also results in phenomenologically simpler reaction kinetics, and overall these features have facilitated a detailed study of linear free energy relationships, kinetic isotope effects, and the first quantitative experimental data on the effects of aryl electron demand and conformational freedom on the rate of reductive elimination from diaryl-gold(III) species. The turnover-limiting step for the formation of a series of fluorene derivatives is sensitive to the reactivity of the arene and changes from reductive elimination to ?-complexation for arenes bearing strongly electron-withdrawing substituents (σ > 0.43). Reductive elimination is accelerated by electron-donating substituents (ρ = -2.0) on one or both rings, with the individual σ-values being additive in nature. Longer and more flexible tethers between the two aryl rings result in faster reductive elimination from Ar-Au(X)-Ar and lead to the ?-complexation of the arene by Ar-AuX2 becoming the turnover-limiting step.

Efficient palladium-catalyzed C(sp2)-H activation towards the synthesis of fluorenes

A facile protocol for the synthesis of fluorene derivatives has been developed through palladium-catalyzed cyclization of 2′-halo-diarylmethanes via activation of arylic C-H bonds. The reactions occurred smoothly and allowed both electron-rich and electron-deficient substrates to convert into their corresponding fluorenes in good to excellent yields. Studies revealed that this Pd-catalyzed cyclization was also available for the substrates of 2′-chloro-diarylmethanes and no catalyst poisoning occurred for 2′-iodo-diphenylmethane.

The transition-metal-catalyst-free oxidative homocoupling of organomanganese reagents prepared by the insertion of magnesium into organic halides in the presence of MnCl2·2LiCl

Organomanganese reagents were prepared by the insertion of magnesium into aryl halides in the presence of MnCl2·2LiCl. These organomanganese reagents smoothly undergo 1,2-addition, acylation, and Pd-catalyzed cross-coupling with various electrophiles. Especially, the oxidative homocoupling of organomanganese reagents was completed in one pot without an additional transition-metal catalyst.

Substitution controlled functionalization of ortho -bromobenzylic alcohols via palladium catalysis: Synthesis of chromenes and indenols

An efficient domino Pd-catalyzed transformation of simple ortho-bromobenzyl tertiary alcohols to chromenes is presented. Their formation is believed to proceed via the formation of a five-membered palladacycle, which, in turn, involves in an intermolecular homocoupling with the second ortho- bromobenzyltertiary alcohol to yield the homo-biaryl bond followed by intramolecular C-O bond formation. Interestingly, when there is an allylic substituent on the benzylic carbon atom, a chemoselective switch was observed, which preferred intramolecular Heck coupling and gave indenols. Further, it has been confirmed that the tertiary alcohol functionality is indispensible to give the coupled products, whereas the use of primary/secondary benzylic alcohols furnished the simple carbonyl products via a possible reductive debromination followed by oxidation due to the availability of β-hydrogen(s).

CuII-catalyzed asymmetric hydrosilylation of diaryl- and aryl heteroaryl ketones: Application in the enantioselective synthesis of orphenadrine and neobenodine

With certain amounts of sodium tert-butoxide and tert-butanol as additives, catalytic amounts of an inexpensive and easy-to-handle copper source Cu(OAc)2·H2O, a commercially available and air-stable non-racemic dipyridylphosphine ligand, as well as the stoichiometric desirable hydride donor polymethylhydrosiloxane (PMHS), formed a versatile in situ catalyst system for the enantioselective reduction of a broad spectrum of prochiral diaryl and aryl heteroarylketones in air, in high yields and with good to excellent enantioselectivities (up to 96 %). In particular, the practical viability of this process was evinced by its successful applications in the asymmetric synthesis of optically enriched potent antihistaminic drugs orphenadrine and neobenodine. Copyright

Fluorenone synthesis by palladacycle-catalyzed sequential reactions of 2-bromobenzaldehydes with arylboronic acids

Chemical equations presented. A new, anionic four-electron donor-based (type I) palladacycle-catalyzed sequential reaction of 2-bromobenzaldehydes with arylboronic acids based on the addition reaction, cyclization via C-H activation-oxidation sequence is described. Our study provided an efficient access to a variety of substituted fluorenones/indenofluorenediones from readily available arylboronic acids and 2-bromobenzaldehydes.

Synthesis of 1,3-Diaryl-2-methoxyindenes by hydriodic acid-catalyzed cyclization of Aryl[2-(1-aryl-2-methoxyvinyl)phenyl]methanols

An efficient two-step method for the synthesis of 1,3-diaryl-2- methoxyindenes from 1-(1-aryl-2-methoxyvinyl)-2-bromobenzenes has been developed. Thus, the reaction of 2-(1-aryl-2-methoxyvinyl)phenyllithiums, generated in situ by halogen-lithium exchange between 1-(1-aryl-2-methoxyvinyl)- 2-bromobenzenes and butyllithium, with aromatic aldehydes gives aryl[2-(1-aryl-2-methoxyvinyl)phenyl]methanols, which in turn are treated with a catalytic amount of concentrated hydriodic acid to afford the corresponding 1,3-diaryl-2-methoxyindenes in reasonable yields.

Photoinduced C-Br homolysis of 2-bromobenzophenones and Pschorr ring closure of 2-aroylaryl radicals to fluorenones

(Chemical Equation Presented) A variety of diversely substituted 2-aroylaryl radicals, generated by photoinduced homolysis of 2-bromoarylketones, is shown to undergo Pschorr cyclization to yield fluorenones in moderate to excellent yields. The photochemical results illustrate that the substituents in the two phenyl rings of the 2-bromobenzophenone skeleton exert a dramatic influence on the reactivity of the derived 2-aroylaryl radicals. The disubstitution by methoxy groups in the radical ring renders the aryl σ-radical highly electrophilic and unreactive for hydrogen abstraction and cyclization. On the other hand, the substituents in the non-radical ring that strongly stabilize the hydrofluorenyl π-radical, formed subsequent to the attack of the 2-aroylaryl radical on the non-radical ring, promote cyclization to furnish fluorenones in excellent isolated yields.

Selective serotonin receptor antagonists and therapeutic applications thereof

Spiro[9,10-dihydroanthracene]-9,3′-pyrrolidine (SPAN) and derivatives thereof are provided as selective serotonin receptor antagonists. The compounds are selective, high affinity antagonists of 5-HT2 serotonin receptors. The compounds are useful as antidepressant and antianxiety agents.