20669-52-7

Upstream product

• 447-53-0 1,2-Dihydronaphthalene 
• 100-56-1 phenylmercury(II) chloride 
• 58719-65-6 (E)-1-styryl-2-vinylbenzene 
• 62019-39-0 2-phenyl-1,2-dihydronaphthalene 
• 85803-91-4 5-phenylbenzobicyclo<3.1.0>hex-2-ene 
• 67504-57-8 (1R*,1aR*,6aR*)-1-phenyl-1,1a,6,6a-tetrahydrocyclopropa[a]indene 
• 67504-57-8 (1SR,1aRS,6aRS)-1-phenyl-1,1a,6,6a-tetrahydrocyclopropa[α]indene 
• 886-65-7 trans,trans-1,4-Diphenyl-1,3-butadiene 
• 591-50-4 iodobenzene 
• 100-59-4 phenylmagnesium chloride 
• 530-93-8 1,2,3,4-tetrahydronaphthalen-2-one 
• 143139-14-4 trifluoromethanesulfonic acid 3,4-dihydronaphthalen-2-yl ester 
• 103-80-0 phenylacetyl chloride 
• 849943-93-7 3,4-dihydronaphthalen-2-yl 4-methylbenzenesulfonate 

Downstream Products

• 612-94-2 2-phenylnaphthalene 
• 135042-37-4 1,1-Dibrom-1a,2,3,7b-tetrahydro-1a-phenyl-1H-cyclopropanaphthalin 
• 62019-39-0 2-phenyl-1,2-dihydronaphthalene 
• 40650-73-5 and 2-phenyl-1,4-dihydronaphthalene 
• 57653-11-9 1-Hydroxy-2-phenyl-1,4-dihydronaphthalin 
• 7498-87-5 2-phenyl-3,4-dihydro-2H-naphthalen-1-one 
• 881851-79-2 (1S,2R)-2-phenyl-1,2,3,4-tetrahydronaphthalen-1-ol 

Relevant academic research and scientific papers

Catalytic 1,2-dihydronaphthalene and: E -aryl-diene synthesis via CoIII-Carbene radical and o -quinodimethane intermediates

Catalytic synthesis of substituted 1,2-dihydronaphthalenes via metalloradical activation of o-styryl N-tosyl hydrazones ((E)-2-(prop-1-en-1-yl)benzene-N-tosyl hydrazones) is presented, taking advantage of the intrinsic reactivity of a cobalt(iii)-carbene radical intermediate. The method has been successfully applied to a broad range of substrates with various R1 substituents at the aromatic ring, producing the desired ring products in good to excellent isolated yields for substrates with an R2 = COOEt substituent at the vinylic position (～70-90%). Changing the R2 moiety from an ester to other substituents has a surprisingly large influence on the (isolated) yields. This behaviour is unexpected for a radical rebound ring-closure mechanism, and points to a mechanism proceeding via ortho-quinodimethane (o-QDM) intermediates. Furthermore, substrates with an alkyl substituent on the allylic position reacted to form E-aryl-dienes in excellent yields, rather than the expected 1,2-dihydronaphthalenes. This result, combined with the outcome of supporting DFT calculations, strongly points to the release of reactive o-QDM intermediates from the metal centre in all cases, which either undergo a 6π-cyclisation step to form the 1,2-dihydronaphthalenes, or a [1,7]-hydride shift to produce the E-aryl-dienes. Trapping experiments using TEMPO confirm the involvement of cobalt(iii)-carbene radical intermediates. EPR spectroscopic spin-trapping experiments using phenyl N-tert-butylnitrone (PBN) confirm the radical nature of the catalytic reaction.

Three-Component Difunctionalization of Cyclohexenyl Triflates: Direct Access to Versatile Cyclohexenes via Cyclohexynes

Difunctionalization of strained cyclic alkynes presents a powerful strategy to build richly functionalized cyclic alkenes in an expedient fashion. Herein we disclose an efficient and flexible approach to achieve carbohalogenation, dicarbofunctionalization, aminohalogenation and aminocarbonation of readily available cyclohexenyl triflates. We have demonstrated the novel use of zincate base/nucleophile system for effective formation of key cyclohexyne intermediates and selective addition of various carbon and nitrogen nucleophiles. Importantly, leveraging the resulting organozincates enables the incorporation of a broad range of electrophilic partners to deliver structurally diverse cyclohexene motifs. The importance and utility of this method is also exemplified by the modularity of this approach and the ease in which even highly complex polycyclic scaffolds can be accessed in one step.

Synthesis of multisubstituted cycloalkenes through carbomagnesiation of strained cycloalkynes

An efficient synthetic method of seven- and six-membered cycloalkenes through the generation of strained cycloalkynes and following carbomagnesiation is described. Further bond formations of the resulting cycloalkenylmagnesium intermediates with a wide variety of electrophiles enabled us to prepare diverse cycloalkene derivatives including benzoxepine analogs having a fully substituted alkene structure.

Bridged Stilbenes: AIEgens Designed via a Simple Strategy to Control the Non-radiative Decay Pathway

To broaden the application of aggregation-induced emission (AIE) luminogens (AIEgens), the design of novel small-molecular dyes that exhibit high fluorescence quantum yield (Φfl) in the solid state is required. Considering that the mechanism of

Gold(I)-Catalyzed Intramolecular C(sp3)?H Insertion by Decarbenation of Cycloheptatrienes

A novel synthesis of indanes and dihydronaphtalenes based on the intramolecular insertion into C(sp3)?H bonds of gold(I) carbenes generated by retro-Buchner reaction (decarbenation) has been developed. Deuterium-labeling and kinetic isotope effect experiments, DFT calculations, and generation of the proposed carbene intermediate from a well-characterized gold(I) carbenoid support the involvement of a three-center concerted mechanism for the C(sp3)?H functionalization process.

Conversion of Carbonyl Compounds to Olefins via Enolate Intermediate

A general and efficient protocol to synthesize substituted olefins from carbonyl compounds via nickel catalyzed C—O activation of enolates was developed. Besides ketones, aldehydes were also suitable substrates for the presented catalytic system to produce di- or tri- substituted olefins. It is worth noting that this approach exhibited good tolerance to highly reactive tertiary alcohols, which could not survive in other reported routes for converting carbonyl compounds to olefins. This method also showed good regio- and stereo-selectivity for olefin products. Preliminary mechanistic studies indicated that the reaction was accomplished through nickel catalyzed C—O activation of enolates, thus offering helpful contribution to current enol chemistry.

Sulfones as Synthetic Linchpins: Transition-Metal-Free sp3–sp2 and sp2–sp2 Cross-Couplings Between Geminal Bis(sulfones) and Organolithium Compounds

A valuable umpolung strategy that highlights the ambiphilic nature of the bis(phenylsulfonyl)methyl synthon and demonstrates its utility as a synthetic linchpin is reported. Although the bis(phenylsulfonyl)methyl group is typically introduced as an sp3-carbon nucleophile, it is demonstrated that it can also function as an effective sp2-carbon electrophile in the presence of organolithium nucleophiles. Alkyl- and aryllithiums couple with the central carbon of the bis(phenylsulfonyl)methyl unit to ultimately generate trisubstituted alkenes, comprising formal sp3–sp2 and sp2–sp2 cross-couplings between organolithium reagents and bis(sulfones). This process occurs almost instantaneously at ?78 °C in the absence of any transition metals. By developing this curious transformation, it has been demonstrated that bis(phenylsulfonyl)methane is a valuable synthetic linchpin, which can undergo two C?C bond-forming processes as an sp3-nucleophile, followed by a third C?C bond-forming reaction as an effective sp2-electrophile. This discovery significantly enhances the utility of this ubiquitous, but underutilized, linker group.

ALKENES AS ALKYNE EQUIVALENTS IN RADICAL CASCADES TERMINATED BY FRAGMENTATIONS

Disclosed are methods for rerouting radical cascade cyclizations by using alkenes as alkyne equivalents. The reaction sequence is initiated by a novel 1,2 stannyl shift which achieves chemo- and regioselectivity in the process. The radical “hopping” leads to the formation of the radical center necessary for the sequence of selective cyclizations and fragmentations to follow. In the last step of the cascade, the elimination of a rationally designed radical leaving group via β-C—C bond scission aromatizes the product without the need for external oxidant. The Bu3Sn moiety, which is installed during the reaction sequence, allows further functionalization of the product via facile reactions with electrophiles as well as Stille and Suzuki cross-coupling reactions. This selective radical transformation opens a new approach for the controlled transformation of enynes into extended polycyclic structures of tunable dimensions.

Design of leaving groups in radical C-C fragmentations: Through-bond 2c-3e interactions in self-terminating radical cascades

Radical cascades terminated by β-scission of exocyclic C-C bonds allow for the formation of aromatic products. Whereas β-scission is common for weaker bonds, achieving this reactivity for carbon-carbon bonds requires careful design of radical leaving groups. It has now been found that the energetic penalty for breaking a strong σ-bond can be compensated by the gain of aromaticity in the product and by the stabilizing two-center, three-electron "half-bond" present in the radical fragment. Furthermore, through-bond communication of a radical and a lone pair accelerates the fragmentation by selectively stabilizing the transition state. The stereoelectronic design of radical leaving groups leads to a new, convenient route to Sn-functionalized aromatics.

Copper-catalyzed alkene arylation with diaryliodonium salts

Alkenes and arenes represent two classes of feedstock compounds whose union has fundamental importance to synthetic organic chemistry. We report a new approach to alkene arylation using diaryliodonium salts and Cu catalysis. Using a range of simple alkenes, we have shown that the product outcomes differ significantly from those commonly obtained by the Heck reaction. We have used these insights to develop a number of new tandem and cascade reactions that transform readily available alkenes into complex arylated products that may have broad applications in chemical synthesis.