2,2′-Bis(arylamino)-1,1′-biaryls as Building Blocks for the Synthesis of Dibenzo[d,f][1,3]diazepines,Dibenzo[d,f][1,3]diazepinones,and Dibenzo[c,e][1,2,7]thiadiazepine 6-Oxides

The iron-catalyzed oxidative C−C homocoupling of diarylamines affords 2,2′-bis(arylamino)-1,1′-biaryls which represent crucial synthetic building blocks for an access to a range of seven-membered heterocyclic ring systems. Reaction with paraformaldehyde, diphenyl carbonate, and diphenyl sulfite as efficient 1,1-dielectrophiles led to dibenzo[d,f][1,3]diazepines, dibenzo[d,f][1,3]diazepinones, and dibenzo[c,e][1,2,7]thiadiazepine 6-oxides. The synthetic procedures enable short and practical routes to these 1,3-diazepine derivatives under mild reaction conditions and with a high tolerance of various functional groups.     

Synthesis and resolution of 2,2′-bis[di(p-tolyl)stibano]-1,1′-binaphthyl (BINASb); the first example of an optically active organoantimony ligand for asymmetric synthesis

Racemic 2,2′-bis[di(p-tolyl)stibano]-1,1′-binaphthyl (BINASb) (±)-2 has been prepared from 2,2′-dibromo-1,1′-binaphthyl 1 via 2,2′-dilithio-1,1′-binaphthyl intermediate, and has been resolved via the separation of a mixture of the diastereomeric Pd complexes 4A and 4B, derived from the reaction of (±)-2 with di-μ-chlorobis{(S)-2-[1-(dimethylamino)ethyl]phenyl-C,N}dipalladium(II) 3. The optically active BINASbs (S)-(+)-2 and (R)-(−)-2 have been shown to be effective chiral ligands for the rhodium-catalyzed asymmetric hydrosilylation of ketones.     

Intramolekulare Cycloaddition von [1,1′-Binaphthyl]-2,2′-bis(allylamin)

Intramolecular cycloaddition of [1,1′-binaphthyl]-2,2′-bis(allylamine) Unlike the 1,1′-binaphthyl-2,2′-bis(allylether) the corresponding [1,1′-binaphthyl]-2,2′-bis(allylamine) (1) upon heating to 230° in mesitylene undergoes thermal decomposition only. However, when 1 is heated in a mixture of 2-methylaminoethanol and water, besides 3 the policyclic ketones 4 and 5 are formed in isolated yields of 28 and 10%, respectively (Scheme 1). Intermediates are the imines corresponding to 4 and 5 which are hydrolysed under the reaction conditions rather than decomposed. The imines are formed by a intramolecular Diels-Alder reaction, in which the double bond of one N-allylgroup reacts with the naphthalene ring of the second half of the molecule. The policyclic ketones 4 and 5 are characterized as acetates 6 and 7 , respectively, and as the acetylated reduced products 11 , and 12 and 13 , respectively. The constitutions of all compounds are derived from spectroscopic data, chiefly from the ¹H-NMR. spectra.     

Dibenzo[d,f][1,3] dioxepine derivatives: A review

This review presents a survey of synthetic methods and reaction mechanism of the dibenzo[d,f][1,3] dioxepine derivatives. Furthermore, the influence of the substituent groups in 6,6′‐position of dibenzo[d,f][1,3] dioxepine on their conformation is explored. The functional dibenzo[d,f][1,3] dioxepine synthetically versatiles substrate, as they can be used for synthesis of a large variety of π‐conjugated oligomer and polymer containing heterocyclic compounds, such as dibromination dibenzo[d,f][1,3] dioxepine derivative as a raw material of synthesis for organic semiconductor polymers. The synthetic and fluorescent property of π‐conjugated polymers basic on dibenzo[d,f][1,3] dioxepine also is explored. J. Heterocyclic Chem., (2012).     

New optically active organoantimony (BINASb) and bismuth (BINABi) compounds comprising a 1,1′-binaphthyl core: synthesis and their use in transition metal-catalyzed asymmetric hydrosilylation of ketones

Racemic 2,2′-bis[diarylstibano]-1,1′-binaphthyls [(±)-BINASbs] and 2,2′-bis[di(p-tolyl)bismuthano]-1,1′-binaphthyl [(±)-BINABi], which are the antimony and bismuth congeners of BINAP, have been prepared from 2,2′-dibromo-1,1′-binaphthyl (DBBN) via 2,2′-dilithio-1,1′-binaphthyl intermediate by treatment with the appropriate metal halides [(p-Tol)₂SbBr, Ph₂SbBr and (p-Tol)₂BiCl]. The optical resolution of the (±)-BINASbs could be achieved via the separation of a mixture of the diastereomeric Pd-complexes derived from the reaction of (±)-BINASbs with di-μ-chlorobis{(S)-2-[1-(dimethylamino)-ethyl]phenyl-C¹,N}dipalladium(II). Optically active (R)-BINASb and (R)-BINABi could be also obtained from optically active (R)-DBBN by the same procedure. The enantiopure BINASbs have been shown to be effective chiral ligands for the rhodium-catalyzed asymmetric hydrosilylation of ketones.     

Reaction of sulfenes with heterocyclic N,N-disubstituted α-aminomethyleneketones. XII. Synthesis of [1]benzothiepino[4,5-e][1,2]oxathiin derivatives

The 1,4-cycloaddition of sulfene to N,N-disubstituted (E)-4-aminomethylene-3,4-dihydro[1]benzothiepin-5(2H)-ones I occurred only in the case of aliphatic N,N-disubstitution to give in good yield 4-dialkylamino-3,4,5,6-tetrahydro[1]benzothiepino[4,5-e][1,2]oxathiin 2,2-dioxides, which are derivatives of the new heterocyclic system [1]benzothiepino[4,5-e][1,2]oxathiin. Also the reaction of I with chlorosulfene occurred only in the case of aliphatic N,N-disubstitution to afford chiefly trans-4-dialkylamino-3-chloro-3,4,5,6-tetrahydro-[1]benzothiepino[4,5-e][1,2]oxathiin 2,2-dioxides III in satisfactory yield. Adducts III were dehydrochlorinated with DBN to 4-dialkylamino-5,6-dihydro[1]benzothiepino[4,5-e][1,2]oxathiin 2,2-dioxides in good yield.     

Eight-membered organosulfur heterocycles. Synthesis of dibenzo[d,g][1,3,6,2]dioxathiaphosphocin and dibenzo[d,g][1,3,6,2]dioxathiasilocin ring systems

The reaction of 2,2′-thiobisphenols with either phenylphosphonous dichloride or phosphorus trichloride followed by an alcohol gave derivatives of the dibenzo[d,g][1,3,6,2]dioxathiaphosphocin ring system. The analogous reaction of 2,2′-thiobisphenols with alkyl and aryl dichlorosilanes gave the heretofore unreported dibenzo[d,g][1,3,6,2]dioxathiasilocin ring system. The analytical and spectral data are reported.     

Synthesis and X-ray structures of rhodium complexes with new chiral biaryl-based NHC-ligands

A new series of chiral NHC–rhodium complexes has been prepared from the reactions between [Rh(COD)Cl]₂, NaOAc, KI and dibenzimidazolium salt 4a or monobenzimidazolium salts 4b–d, which are derived from chiral 2,2′-diamino-6,6′-dimethyl-1,1′-biphenyl, 2,2′-diamino-1,1′-binaphthyl or 6,6′-dimethyl-2-amino-2′-hydroxy-1,1′-biphenyl. The steric and electronic effects of the ligand play an important role in the complex formation. For example, treatment of chiral monobenzimidazolium salt 4b (with a NMe₂ group) with 0.5 equiv of [Rh(COD)Cl]₂ in the presence of NaOAc and KI in CH₃CN at reflux gives a chiral Rh(I) complex 5b, while chiral monobenzimidazolium salt 4d (with a MeO group) affords a racemic Rh(I) complex 5d. Under similar reaction conditions, treatment of dibenzimidazolium salt 4a with 0.5 equiv of [Rh(COD)Cl]₂ in the presence of NaOAc and KI gives a racemic Rh(III) complex 5a, while the dibenzimidazolium salt [C₂₀H₁₂(C₇H₅N₂Me)₂]I₂ derived from chiral 2,2′-diamino-1,1′-binaphthyl affords a chiral Rh(III) complex [C₂₀H₁₂(C₇H₄N₂Me)₂]RhI₂(OAc). All compounds have been characterized by various spectroscopic techniques, and elemental analyses. The solid-state structures of the rhodium complexes have been further confirmed by X-ray diffraction analyses.     

Syntheses of helical polymers through the combination of axially dissymmetric segments

Wholly aromatic polymers with various helical structures were prepared through the combination of two axially dissymmetric bifunctional compounds. The palladium-catalyzed condensation of (R)-2,2-diethoxy-6,6′-dibromo-1,1′-binaphthyl with (R)-1,1′-binaphthyl-2,2′-diamine and the reaction of (S)-2,2-diethoxy-6,6′-dibromo-1,1′-binaphthyl with (S)-1,1′-binaphthyl-2,2′-diamine produced helical polyamines, and the chiral conformation was confirmed by their circular dichroism spectra and large specific rotations. The combination of (R)-2,2-diethoxy-6,6′-dibromo-1,1′-binaphthyl and (S)-1,1′-binaphthyl-2,2′-diamine afforded polyamines with a zigzag conformation. The condensation of (R)-2,2′-dimethylbiphenyl-6,6′-dicarbonyl chloride with (R)-2,2′-diamino-6,6′-dimethylbiphenyl and the reaction of (S)-2,2′-dimethylbiphenyl-6,6′-dicarbonyl chloride with (S)-2,2′-diamino-6,6′-dimethylbiphenyl predominantly yielded cyclic dimers and tetramers because of the steric proximity of the reactive groups of the propagating species. The experimental results indicated that the structures of the obtained polymers depended on the combination of the chirality of the bifunctional atropisomeric compounds and the position of the functional groups on the aromatic rings. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4607–4620, 2004     

Chiral nematic liquid crystals with helix inversion from (R)-1,1′-binaphthyl and cholesteryl ester moieties

In this study, on the concept of intramolecular chiral conflict between the (R)-1,1′-binaphthyl and cholesteryl ester moieties, we have designed and synthesised a new liquid crystal (LC) (R)-dicholesteryl 6,6′-[1,1′-binaphthyl-2,2′-diylbis(oxy)]dihexanoate [(R)-DC]. A helix inversion could be observed for the chiral nematic liquid crystal (N*-LC) comprising the commercial nematic LC (N-LC) host SLC1717 and (R)-DC on heating. As a comparison, (S)-dicholesteryl 6,6′-[1,1′-binaphthyl-2,2′-diylbis(oxy)]dihexanoate [(S)-DC] was also prepared. Due to the intramolecular chiral superposition between the (S)-1,1′-binaphthyl and cholesteryl ester moieties, the N*-LC comprising SLC1717 and (S)-DC also exhibited excellent temperature sensitivity.     

Synthesis of diallyl‐containing polyimide and the effect of allyl groups on properties

A diallyl‐containing bisphenol, 1,1‐bis(3‐allyl‐4‐hydroxyphenyl)‐1‐(6‐oxido‐6H ‐dibenzo [c,e][1,2] oxaphosphorin‐6‐yl) ethane ( 1 ), was prepared by a two‐step procedure. Then, a diallyl‐containing diamine, 1,1‐bis(3‐allyl‐4‐(4‐aminophenoxy)‐phenyl)‐1‐(6‐oxido‐6H‐dibenzo [c,e][1,2] oxaphosphorin‐6‐yl)ethane ( 3 ), was prepared from the nucleophilic substitution of ( 1 ) with 4‐fluoronitrobenzene, followed by the reduction by Fe/HCl. A flexible polyimide ( 4 ) with curable diallyl linkages was prepared from the condensation of ( 3 ) and 4,4′‐oxydiphthalic anhydride in m‐cresol in the presence of isoquinoline. Curing polyimide ( 4 ) at 300 °C leads to thermosetting polyimide ( 5 ). We discussed the amounts of allyl group on T_g, coefficient of thermal expansion, and thermal stability of thermosetting polyimides, and found that thermal properties and dimensional stability of thermosetting polyimides increase with the amounts of cured allyl moieties. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 513–520     

Coupling of iodonaphthalenes with naphthoxide ions under SRN1 conditions. Synthesis of unsymmetrical binaphthyl derivatives.

Unsymmetrical 1,1′-, 1,2′- and 2,2′-binaphthyl derivatives are obtained by a one-step coupling reaction of variously substituted moieties: naphthoxides and iodonaphthalenes; an S_RN1 mechanism is proposed.     

Spiro Compounds of Tin,Selenium and Tellurium Containing 1,3,2‐Diazaelement‐[3]ferrocenophane Units

The reactions of 1,1′‐bis[Li(trimethylsilyl)amino]ferrocene ( 2a ) with selenium‐ or tellurium tetrahalides gave the 1,1′,3,3′‐tetrakis(trimethylsilyl)‐1,1′,3,3′‐tetraaza‐2‐selene‐ and 2‐tellura‐2,2′‐spirobi[3]ferrocenophanes 5 and 6 , respectively. The analogous reaction with tin dichloride afforded the corresponding 2‐stanna‐2,2′‐spirobi[3]ferrocenophane ( 9 ) rather than the expected stannylene 8 . The reaction of 2,2‐dichloro‐1,3‐bis(trimethylsilyl)‐1,3,2‐diazastanna‐[3]ferrocenophane ( 10 ) with the dilithio reagent 2b also gave the spirotin compound 9 , of which the molecular structure was determined by X‐ray analysis. The formation of the products and their solution‐state structures was deduced from multinuclear magnetic resonance spectroscopic studies (¹H, ¹³C, ¹⁵N, ²⁹Si, ⁷⁷Se, ¹²⁵Te, ¹¹⁹Sn NMR spectroscopy).     

Enantioselective Synthesis of Distorted π-Extended Chiral Triptycenes Consisting of Three Distinct Aromatic Rings by Rhodium-Catalyzed [2+2+2] Cycloaddition

The enantioselective synthesis of distorted π-extended chiral triptycenes, consisting of three distinct aromatic rings, has been achieved with high ee value of 87 % by the cationic rhodium(I)/segphos complex-catalyzed enantioselective [2+2+2] cycloaddition of 2,2′-di(prop-1-yn-1-yl)-5,5′-bis(trifluoromethyl)-1,1′-biphenyl with 6-methoxy-1,2-dihydronaphthalene followed by the diastereoselective Diels–Alder reaction and aromatization. Demethoxy derivatives were also synthesized by the C−O bond cleavage. In this synthesis, the use of the electron-deficient diyne and the electron-rich alkene is crucial to suppress the undesired strain-relieving carbocation rearrangement and stabilize the distorted triptycene structure.     

Halogenation and nitration of naphtho[1,2-c][1,2,5]thiadiazole

Bromination of naphtho[1,2-c][1,2,5]thiadiazole ( I ) gives either an addition product, 4,5-dibromo-4,5-dihydronaphtho[1,2-c][1,2,5]thiadiazole ( II ), or a substitution product, 5,6-dibromonaphtho[1,2-c][1,2,5]thiadiazole ( III ), depending on the reaction conditions. Dehydrobromination of II gives 5-bromonaphtho[12-c][1,2,5]thiadiazole ( IV ). Chlorination of I gives the corresponding addition product V or 5-chloronaphtho[1,2-c][1,2,5]thiadiazole ( VI ). Compound VI can also be obtained by dehydrochlorination of V. The nitration of I produces a mixture of isomeric substitution products, 9-nitro VIII and 6-nitronaphtho[1,2-c][1,2,5]thiadiazoles ( VII ).     

Synthesis of some pyrazolo[4,3-e][1,2]- and thiazolo[4,5-e][1,2]thiazine 1,1-dioxide derivatives

The synthesis of various 2-methylpyrazolo[4,3-e]- and thiazolo[4,5-e][1,2]thiazine 1,1-dioxide derivatives is described.     

An Efficient Synthesis of 3,3′,4,4′‐Tetrahydro‐4,4′‐bibenzo[e][1,3]oxazine‐2,2′‐dione Derivatives with the Aid of Low‐valent Titanium

Synthesis of 3,3′,4,4′‐tetrahydro‐4,4′‐bibenzo[e][1,3]oxazine‐2,2′‐diones via reaction of salicylidendphenylhydrazone and triphosgene with the aid of low‐valent titanium reagent is described. This method has the advantages of accessible starting materials, good yields and short reaction time.     

C2-Symmetric sulfur derivatives of 2,2′,3,3′-tetramethoxybiphenyl

A practical route to prepare dithioether, thiophene and thiophene S-dioxide derivatives of 2,2′,3,3′-tetramethoxy-1,1′-biphenyl 1 is described. Resolution of 6,6′-bis(methylthio)-3,3′-dimethoxy-[1,1′-biphenyl]-2,2′-diol 15 was achieved and its absolute configuration was assigned by X-ray analysis of the corresponding phosphorothioamidate diastereomer 18.     

Synthesis of some 2-(heteroarylamino)benzimidazoles and their cyclization with phosgene

2-(Benzimidazol-2-ylamino)pyridine (4a) , 2-(benzimidazol-2-ylamino)pyrazine (4b) , and 2-(benzimidazol-2-ylamino)thiazole (4c) underwent a ring-closure reaction on treatment with phosgene affording 6H-pyrimido-[1′,2′:5,4][1,3,5]triazino[1,2-a]benzimidazol-6-one (1a) , 6H-pyrazino[1′,2′:5,4][1,3,5]triazino[1,2-a]benzimidazol-6-one (1b) , and 5H-thiazolo[2′,3′:4,5][1,3,5]triazino[1,2-a]benzimidazol-5-one (1c) respectively. The structure of these hitherto unknown heterocyclic systems was confirmed by their ir and mass spectra.     

Synthesis of novel spiro[indole-3,3′-pyrrolidin]-2(1H)-ones

Diastereoselective [3+2] cycloaddition of azomethine ylide to 1,3-dimethyl-6-(2-oxo-1,2-dihydro-3H-indol-3-ylidene)-3a,9a-diphenyl-3,3a,9,9a-tetrahydroimidazo[4,5-e]thiazolo[3,2-b]-[1,2,4]triazine-2,7(1H,6H)-dione yields hitherto unknown 1,1′,3-trimethyl-3a,9a-diphenyl-3,3a,9,9a-tetrahydrodispiro(imidazo[4,5-e]thiazolo[3,2-b][1,2,4]triazine-6,3′-pyrrolidine-4′,3″-indole)-2,2″,7(1H,1″H)-triones.