2430-34-4

Upstream product

• 21473-01-8 2-naphthalenylmagnesium bromide 
• 98299-22-0 <2-D>-1,2-Dihydronaphthalin 
• 73073-35-5 <2,2-D₂>-1,2-Dihydronaphthalin 
• 73073-31-1 2>-1,2-Dihydronaphthalin 
• 73073-31-1 2>-1,2-Dihydronaphthalin 
• 580-13-2 2-bromonaphthalene 
• 91-58-7 2-chloronaphthalene 
• 1503-86-2 2-naphthyl pivalate 
• 135-19-3 β-naphthol 
• 811-98-3 d⁽⁴⁾-methanol 
• 612-55-5 2-iodonaphthalene 
• 100-58-3 phenylmagnesium bromide 
• 7698-05-7 hydrogen chloride 
• 95386-58-6 (1-4a,8a-η-{2-D}naphthalene)Cr(CO)3 

Downstream Products

• 91-20-3 naphthalene 

Relevant academic research and scientific papers

Chemoselective Cross-Coupling between Two Different and Unactivated C(aryl)-O Bonds Enabled by Chromium Catalysis

We report here the first example of cross-coupling between two different and unactivated C(aryl)-O bonds with chromium catalysis. The combination of a low-cost Cr(II) salt, 4,4′-di-tert-butyl-2,2′-dipyridyl (dtbpy) as the ligand, and magnesium as the reductant shows high reactivity in promoting the reductive cross-coupling of aryl methyl ether derivatives with aryl esters by cleavage and coupling of two different C(aryl)-O bonds under mild conditions. The formation of active low-valent Cr species by reduction of CrCl2 with Mg can be considered, which prefers to initially activate the C(aryl)-O bond of phenyl methyl ether with the chelation help of dtbpy and an o-imine auxiliary. The subsequent consecutive reduction, second C(aryl)-O activation, and reductive elimination allow for the achievement of selective cross-coupling of C(aryl)-O/C(aryl)-O bonds.

Metal-Free sp2-C-H Borylation as a Common Reactivity Pattern of Frustrated 2-Aminophenylboranes

C-H borylation is a powerful and atom-efficient method for converting affordable and abundant chemicals into versatile organic reagents used in the production of fine chemicals and functional materials. Herein we report a facile C-H borylation of aromatic and olefinic C-H bonds with 2-aminophenylboranes. Computational and experimental studies reveal that the metal-free C-H insertion proceeds via a frustrated Lewis pair mechanism involving heterolytic splitting of the C-H bond by cooperative action of the amine and boryl groups. The adapted geometry of the reactive B and N centers results in an unprecedentently low kinetic barrier for both insertion into the sp2-C-H bond and intramolecular protonation of the sp2-C-B bond in 2-ammoniophenyl(aryl)- or -(alkenyl)borates. This common reactivity pattern serves as a platform for various catalytic reactions such as C-H borylation and hydrogenation of alkynes. In particular, we demonstrate that simple 2-aminopyridinium salts efficiently catalyze the C-H borylation of hetarenes with catecholborane. This reaction is presumably mediated by a borenium species isoelectronic to 2-aminophenylboranes.

Low-temperature carbon-chlorine bond activation by bimetallic gold/palladium alloy nanoclusters: An application to Ullmann coupling

This paper describes the unique catalytic activity of bimetallic Au/Pd alloy nanoclusters (NCs) for Ullmann coupling of chloroarenes in aqueous media at low temperature. The corresponding reaction cannot be achieved by monometallic Au and Pd NCs as well as their physical mixtures. On the basis of quantum chemical calculation, it was found that the crucial step to govern the unusual catalytic activity of Au/Pd is the dissociative chemisorption of ArCl, which is unlikely in the monometallic Au and Pd NCs.

Cross-coupling of aryl grignard reagents with aryl iodides and bromides through SRN1 pathway

Game, SET, and match: Aryl Grignard reagents undergo coupling with aryl halides when toluene is used as a solvent in combination with a small amount of tetrahydrofuran (see scheme). The reaction proceeds through an SRN1 mechanism, and does not require any transition metal catalysts.

Unexpected formation of aryl ketones by palladium-catalyzed coupling of aryl bromides with vinylic acetates

A palladium-catalyzed coupling reaction of aryl bromides with vinylic acetates in the presence of tributyitin methoxide has been described. Unexpected formation of aryl ketones was obtained. Preliminary mechanistic studies indicated that the reaction proceeded by the addition of the aryl moiety in the coordination sphere of palladium to a ketene.

Addition and cyclization reactions in the thermal conversion of hydrocarbons with an enyne structure, 5: High-temperature ring closures of 1,3-hexadien-5-ynes to naphthalenes - Competing reactions via isoaromatics, alkenylidene carbenes, and vinyl-type radicals

The 4-substituted 1-phenyl-1-butene-3-ynes 1a-c and the 2-ethynylstyrenes 7a-c were subjected to high-temperature pyrolysis. The cycloisomerization products isolated suggest that these are formed by three competing processes: by (i) an electrocyclic or a molecule-induced, (ii) an alkenylidene carbene controlled, and (iii) a radical-controlled ring-closure . To estimate the relative importance of these three reactions here mentioned, the substrates have been isomerized in oxygen-free nitrogen and in nitrogen proportionally substituted by toluene at 700 and 650°C, respectively. The relative contributions of these isomerizations depend not only on the conversion temperature but also on the substituent R in 1 or 7. Wiley-VCH Verlag GmbH, 1997.

Regioselective electrophilic substitution via lithiation and intramolecular arene exchange (haptotropic rearrangement) in (naphthalene)tricarbonylchromium

The sequential reaction of (η6-naphthalene)tricarbonylchromium (1) with (tetramethylpiperidyl)lithium (TMPLi) and electrophiles (D+, ClSiMe3, CO2, MeI, EtOSO2CF3) is highly regioselective and exclusively yields (2-substituted naphthalene)tricarbonylchromium complexes bearing the substituent in the coordinated ring. With n-BuLi, the same sequence gives mixtures of the 1- and 2-substituted naphthalene complexes in the ratio of 3:7. [1-4a,8a-η-1,3-(SiMe3)2C10H 6]Cr(CO)3 (5) is obtained in reactions with excess TMPLi and ClSiMe3. The selectively labeled complexes (1-4a,8a-η-[2-D]naphthalene)Cr(CO)3 (3a) and (1-4a,8a-η-[1,3-8-D7]naphthalene)Cr(CO)3 (3b) were used in a kinetic study of the haptotropic rearrangement of (naphthalene)tricarbonylchromium. The rate constants and activation parameters of the rearrangement in cyclohexane-d12 and in benzene were determined by 1H and 2H NMR methods. In cyclohexane, the activation parameters for the intramolecular rearrangement in 3b were found to be ΔH? = 20.4 kcal mol-1 and ΔH? = -23 cal mol-1 K-1. Haptotropic rearrangement was found to proceed by first-order kinetics and, within experimental error limits, at the same rate in benzene as in cyclohexane. Addition of THF accelerated intra- as well as intermolecular arene exchange. In benzene, at 100°C, the intramolecular ring migration of 3b is 9 times faster than arene exchange. (1-4a,8a-η-2-Methylnaphthalene)Cr(CO)3 (3e) rearranges (ΔH? = 26.2 kcal mol-1) on heating in cyclohexane to an equilibrium mixture (65:35) of the two isomers, the major isomer being the one in which the metal is coordinated to the substituted ring.

Hydrogen Transfer Reactions, 7. Regio- and Stereoselectivity in the Dehydrogenation Steps during Homogeneously Catalysed Hydrogen Transfer

In the disproportionation of 1,2-dihydronaphthalene catalysed by metal complexes, especially by the Wilkinson catalyst (7), the elimination occurs in two steps.The abstraction of the first hydrogen proceeds with but a small preference for the 2-position - in contrast to dehydrogenations via hydride transfer.The second hydrogen is removed highly stereospecifically from the vicinal cis-position, the acceptor being cis-hydrogenated.Intermolecular H/D-scrambling may occur via allyl hydrido complexes.

Hydrogen Transfer Reactions, 6. Dehydrogenation of 1,2-Dihydroarenes by Quinones: Regio- and Stereoselectivity in the Two-Step Mechanism

1,2-Dihydronaphthalene (1) is dehydrogenated by o- and p-quinones in a two-step mechanism.In the rate determining step a hydride ion is abstracted from the 2-position by o-chloro- (4a) and o-bromoanil (4b) with high regioselectivity.Ion pairing leads to highly stereoselective cis-elimination of the proton.Stereoselectivity, primary isotope effects, and activation entropy are consistent with a coplanar coordination in the transition state and participation of tunneling. p-Quinones show different regioselectivity in the hydride abstraction step.The dehydrogenation of 9,10-dihydrophenanthrene (3) proceeds in a similar way.