127760-83-2Relevant academic research and scientific papers
Michael Reaction Inspired Atroposelective Construction of Axially Chiral Biaryls
Li, Shaoyu,Song, Qiuling,Tan, Bin,Xia, Wang,Xiang, Shao-Hua,Yan, Shengyi
, p. 7322 - 7327 (2020)
The first copper-catalyzed atroposelective Michael-type addition between azonaphthalenes and arylboronic acids for the construction of biaryl atropisomers was established using a novel BINOL-derived phosphoramidite as a chiral ligand. A broad range of atropisomeric biaryls were obtained with good efficiency, and the practicality of this approach was verified by versatile transformations toward axially chiral ligands, catalysts, and other functional atropisomers. This set of catalytic systems successfully inhibited the routine 1,2-addition and promoted the formation of an aryl-aryl chiral axis. Meanwhile, this strategy bypassed the use of an oxidant as well as the harsh conditions normally necessary for transition-metal-mediated arene C-H coupling with arylboronic acids as an arylation counterpart, offering a straightforward alternative to access optically active biaryls.
Studies in Stereochemistry. 47. Asymmetric Induction by Leaving Group in Nucleophilic Aromatic Substitution
Wilson, Janet M.,Cram, Donald J.
, p. 4930 - 4943 (1984)
We report here the first examples of transfer of asymmetry from a leaving group to a biaryl product in nucleophilic, aromatic substitution reactions.Chiral products 2--4,4-dimethyl-Δ2-oxazoline (6), 2--4,4-dimethyl-Δ2-oxazoline (8), and 2--4,4-dimethyl-Δ2-oxazoline (11) were produced in high to medium optical yields by aryl-aryl coupling reactions in which 1-naphthyllithium, 3-methoxy-2-naphthyllithium, or 2-methoxy-1-naphthylmagnesium bromide was treated with 2--4,4-dimethyl-Δ2-oxazolines 15-19.The alkoxy leaving groups of the naphthyloxazolines were derived from the naturally occuring alcohols l-menthol, quinine, quinidine, α-fenchol, and borneol.The oxazoline group activates the aromatic nucleus toward nucleophilic aromatic substitution by stabilizing the transition states leading to and from ?-complex intermediates.These reaction intermediates are diastereomeric and are therefore of unequal free energy.Thus one enantiomeric product is formed faster than the other.The configurations of starting materials and products (with the exception of 11) were established by converting them to compounds of established absolute configuration.The optical yields in the 14 reactions examined ranged from ca. >95percent to 8percent and the chemical yields from 88percent to 7percent.The l-menthoxy leaving group gave the highest chiral transfer efficiences (percent chemical yield x optical yield), which ranged from 65percent to 41percent.The more spherical, least dissymmetric α-fenchoxy and bornoxy groups gave the lowest optical yields (77-8percent ee) but rather good chemical yields (88-65percent).The quininoxy and quinidinoxy group produced the most consistently high optical yields (94-80percent ee) but the lowest chemical yields (7-27percent).These two leaving groups gave products of opposite configurations in the three systems examined.The highest value observed for the difference in free energy of the diastereomeric transition states was Δ(ΔG excit.)=2.4 kcal mol-1 and involved 2-methoxy-1-naphthylmagnesium bromide as nucleophile, quininoxy as leaving group, and 8 as product.Unlike most covalently bound chiral auxilliary units used for asymmetric induction in organic synthesis, those of the current study are displaced during the reaction.The direction of the configurational biases is interpreted in terms of the superposition of steric effects on the tendency of the lithium and magnesium ions to be ligated internally in the ?-complex intermediates.
Asymmetric Suzuki-Miyaura cross-coupling of 1-bromo-2-naphthoates using the helically chiral polymer ligand PQXphos
Akai, Yuto,Konnert, Laure,Yamamoto, Takeshi,Suginome, Michinori
, p. 7211 - 7214 (2015)
A single-handed helical polymer ligand PQXphos afforded axially chiral biaryl esters with high enantioselectivities in asymmetric Suzuki-Miyaura cross-coupling. The use of naphthyl bromide bearing a 2,4-dimethyl-3-pentyl ester resulted in both high yields and high enantioselectivities. Either enantiomer could be synthesized selectively by using a single PQXphos through a solvent-dependent switch of the helical chirality. This journal is
Chiral Ligand-Mediated Nucleophilic Aromatic Substitution of Naphthoic Acids: A Fast and Efficient Access to Axially Chiral Biaryls
Nguyen, Thi Thanh Thuy,Guyon, Hélène,Nguyen, Kim Phi Phung,Boussonnière, Anne,Mortier, Jacques,Castanet, Anne-Sophie
, p. 3829 - 3833 (2020/05/25)
A transition metal-free synthesis of enantioenriched biaryls from aryllithium species has been developed. This approach relies on atropoenantioselective nucleophilic aromatic substitution (SNAr) reaction of unprotected naphthoic acids. The ability of a diverse set of chiral ligands to mediate this transformation has been investigated. 1,2-diether ligands outperform their diamine counterparts and the best enantiocontrol was obtained with readily accessible enantiopure trans-1,2-dimethoxycyclohexane. This SNAr reaction offers an efficient and rapid access to enantioenriched binaphthalenes, phenylnaphthalene, and phenanthrylnaphthalenes (up to 94:6 er).
Synthesis of substituted helicenes by Ir-catalyzed annulative coupling of biarylcarboxylic acid chlorides with alkynes
Kamikawa, Ken,Den, Hiroakira,Tsurusaki, Akihiro,Nagata, Tomoya,Miura, Masahiro
, p. 1069 - 1074 (2018/07/29)
A series of substituted [4] and [5]helicenes were synthesized in moderate to good yields by an Ir-catalyzed annulative coupling of biarylcarboxylic acid chlorides with internal alkynes, which involves facile C-H bond cleavage and decarbonylation. The double annulative coupling of 1, 1′:5′, 1″-ternaphthalene- 2, 2″-dicarboxylic acid dichloride with 4-octyne was also accomplished to give rise to an S-shaped double helicene. Unexpectedly, a π-extended benzofluoranthene-merged [5]- helicene was constructed through the annulative coupling and the successive C(aryl)-C(aryl) bond forming reaction when 1, 1′:4′, 1″-ternaphthalene-2, 2″-dicarboxylic acid dichloride was employed as the substrate. The crystal structure and the optical properties of the latter unique product were also investigated.
Ortho-lithium/magnesium carboxylate-driven aromatic nucleophilic substitution reactions on unprotected naphthoic acids
Aissaoui, Regadia,Nourry, Arnaud,Coquel, Ariane,Dao, Thi Thanh Ha,Derdour, Aicha,Helesbeux, Jean-Jacques,Duval, Olivier,Castanet, Anne-Sophie,Mortier, Jacques
experimental part, p. 718 - 724 (2012/02/16)
Substitution of an ortho-fluoro or methoxy group in 1- and 2-naphthoic acids furnishing substituted naphthoic acids occurs in good to excellent yields upon reaction with alkyl/vinyl/aryl organolithium and Grignard reagents, in the absence of a metal catalyst without the need to protect the carboxyl (CO 2H) group. This novel nucleophilic aromatic substitution is presumed to proceed via a precoordination of the organometallic with the substrate, followed by an addition/elimination.
METHOD FOR PREPARING CHEMICAL COMPOUNDS OF INTEREST BY NUCLEOPHILIC AROMATIC SUBSTITUTION OF AROMATIC CARBOXYLIC ACID DERIVATIVES SUPPORTING AT LEAST ONE ELECTRO-ATTRACTIVE GROUP
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Page/Page column 19-20, (2013/02/27)
Method for preparing carboxylic acid derivatives by aromatic nucleophilic substitution, in which a carboxylic acid derivative having a single carboxyl functional group, or one of the salts thereof, the carboxylic acid derivative having, in the ortho posit
Asymmetric construction of binaphthyl by the chiral diether-mediated conjugate addition of naphthyllithium to naphthalenecarboxylic acid 2,6-di-t-butyl-4-methoxyphenyl ester
Shindo, Mitsuru,Yamamoto, Yasutomo,Yamada, Ken-Ichi,Tomioka, Kiyoshi
experimental part, p. 752 - 754 (2009/12/26)
Two ways for the synthesis of binaphthyl were examined based on a chiral ligand-mediated asymmetric conjugate addition of 1-naphthyllithium to naththalene-2-carboxylic acid 2,6-di-t-butyl-4-methoxyphenyl esters. The one pot method by conjugate addition-el
Asymmetric synthesis of helical poly(quinoxaline-2,3-diyl)s by palladium-mediated polymerization of 1,2-diisocyanobenzenes: Effective control of the screw-sense by a binaphthyl group at the chain-end
Ito, Yoshihiko,Miyake, Toshiyuki,Hatano, Seiji,Shima, Ryoto,Ohara, Takafumi,Suginome, Michinori
, p. 11880 - 11893 (2007/10/03)
Aromatizing polymerization of 1,2-diisocyanobenzene derivatives was mediated by optically active organopalladium(II) complexes bearing 1,1'- binaphth-2-yl groups to give optically active poly(quinoxaline-2,3-diyl)s with varying screw-sense selectivities, which crucially depended upon the substituents on the binaphthyl groups. The most effective catalyst, which has 7'-methoxy-1,1'-binaphthyl group, induced the formation of a single screw- sense. Isolation and structural analyses (single-crystal X-ray diffraction and 1H NMR spectroscopy) of intermediary [oligo(quinoxalinyl)]palladium complexes revealed that the screw-sense selection in the polymerization may be decisively governed by the diastereomeric ratios of the (terquinoxalinyl)palladium(II) complex intermediate.
Facile Synthesis of 1,1'-Binaphthyl-2-carboxylates via Nucleophilic Aromatic Substitution of 1-Methoxy-2-naphthoic Esters by 1-Naphthyl Grignard Reagents
Hotta, Hiroki,Suzuki, Takatsugu,Miyano, Sotaro
, p. 143 - 144 (2007/10/02)
Grignard reagents formed from 1-bromonaphthalenes smoothly displaced the 1-methoxyl group of 1-methoxy-2-naphthoic esters to provide a facile route of 1,1'-binaphthyl-2-carboxylic acids in excellent yields; the reaction of (S)-1-phenylethyl esters caused
