142128-92-5

Usage

Uses

Starting material for the preparation of a variety of 3,3'-substituted binaphthols.

Upstream product

• 13057-19-7 Iodomethyl methyl ether 
• 18531-99-2 (S)-[1,1']-binaphthalenyl-2,2'-diol 
• 109-87-5 Dimethoxymethane 
• 602-09-5 (R)-binaphthol 
• 107-30-2 chloromethyl methyl ether 
• 13185-00-7 (S)-6,6'-dibromo-1,1'-bi-2-naphthol 

Downstream Products

• 189518-78-3 (S)-2,2’-bis(methoxymethoxy)-3,3’-diiodo-1,1’-binaphthalene 
• 1621994-95-3 (S)-3-[1-(4-methoxybenzenesulfonyl)-(4S,5S)-4,5-diphenyl-4,5-dihydro-1H-imidazol-2-yl]-1,1'-binaphthalene-2,2'-diyl hydrogen phosphate 

Relevant academic research and scientific papers

Lanthanide-catalyzed asymmetric 1,3-dipolar cycloaddition of nitrones to alkenes using 3,3′-bis(2-oxazolyl)-1,1′-bi-2-naphthol (BINOL-Box) ligands

New BINOL-derived ligands, 3,3′-bis(2-oxazolyl)-1,1′-bi-2-naphthols (BINOL-Box), bearing chiral bis-oxazoline at the 3,3′-carbons, were synthesized from commercially available 1,1′-bi-2-naphthol (BINOL). With the new ligands obtained, we found that asymmetric 1,3-dipolar cycloaddition reaction of N-benzylidenebenzylamine N-oxide (2) to 3-((E)-2-butenoyl)-1,3-oxazolidin-2-one (1) was catalyzed by BINOL-Box-scandium complexes to give isoxazolidine 3 in high yield with high diastereo- and enantioselectivity. For example, the reaction of 1 with 2 catalyzed by a 6 mol% (S,R)-7d and 5 mol% Sc(OTf)3 complex proceeded to give the endo-3 as the major diastereomer with an endo:exo ratio of 97:3 and 87% ee of the endo-product in the presence of 4 ? molecular sieves. Interestingly, the absolute configuration of the major product was changed according to the kind of additive used.

Synthesis of Enantiomerically Pure Thiocrown Ethers Derived from 1,1'-Binaphthalene-2,2'-diol

Synthetic methodology is given for the preparation of two different types of thiocrown ethrs from optically pure 1,1'-binaphthalene-2,2'-diol (10).The conceptually simplest approach starts from optically pure 10 itself, which is alkylated (4 equiv of K2CO3 in DMF at 110 deg C) with 2-chloroethanol followed by mesylation to provide 2,2'-bis(2-mesyloxy)ethoxy)-1,1'-binaphthyl (14).When allowed to react with ethane-1,2-dithiol, propane-1,3-dithiol, 1,4,7--trithiaheptane, 1,4,8,11-tetrathiaundecane, 2,2-dimethylpropane-1,3-dithiol, 2-(mercaptomethyl)-1-propene-3-thiol, and 1,2-benzenedithiol in the presence of Cs2CO3 in DMF at 60 deg C the corresponding thiocrown ethers 22-25, 28, 30, and 32 are formed in 30-54percent yields.Test reactions were carried out to establish that no racemization occurs during alkylation under these conditions.Reaction of optically pure 10 with tetrahydropyranyl (THP)-protected 3-chloropropanol under similar conditions for the preparation of 14 proceeded more sluggishly but cleanly.Removal of the THP protecting groups afforded 2,2'-bis(3-bromopropoxy)-1,1'-binaphthyl (20), which on reaction with propane-1,3-dithiol, 1,5,9-trithianonane, 2,2-dimethylpropane-1,3-dithiol, 2-(mercaptomethyl)-1-propene-3-thiol, and 1,2-bis(mercaptomethyl)benzene provided the respective thiocrown ethers 26, 27, 29, 31, and 33 in 24-68percent yields.Another class of thiocrown ethers was prepared from optically active 10, which converted via ortho-lithiation to 3,3'-bis(bromomethyl)-2,2'-dimethoxy-1,1'-binaphthyl (39) by means of methylation (K2CO3/CH3I)), ortho-lithiation followed by formylation (n-C4H9Li/N,N,N',N'-tetramethylethylenediamine (TMEDA)/ether followed by DMF and H2O workup) followed by reduction (NaBH4) followed by bromination (PBr3 in C5H5N).Reaction (Cs2CO3 in DMF at 60 deg C) with 1,4,7-trithiaheptane, 1,4,8-trithiaoctane, 1,4,7,10-tetrathiadecane, 1,4,8,11-tetrathiaundecane, and 1,5,10,14-tetrathiatetradecane afforded the corresponding thiocrown ethers 40-44 in 40-75percent yields.Despite repeated attempts using a wide range of reagents, demethylation of the methoxy ether functionalities failed.Attempts to prepare the free phenol derivatives of the latter type of grown ethers by oxuidative coupling of two naphthol units failed.

(S)-2,2′-Bis(methoxymethoxy)[1,1′-binaphthyl]-3,3′- dicarbaldehyde

The two naphthalene rings of the title compound, C26H22O6, are in a transoid conformation. The dihedral angle between the mean planes of the naphthalene rings is large at 107.1 (3)°.

Synthesis of bis(binol) substituted 2,2′-bipyridines and their late transition metal complexes

Bis(BINOL) substituted 2,2′-bipyridines (1a and 1b) have been prepared via a twofold Sonogashira cross-coupling reaction from 3-iodo-2,2′-di(methoxymethoxy)-1,1′-binaphthyl (4) and 5,5′-diethynyl-2,2′-bipyridine (2), which could be synthesised through a palladium mediated homodimerisation using zinc powder as a reducing agent. 1a and 1b form well defined silver(I), copper(I) or zinc(II) complexes [M12]+and [Zn1a2]2+ thereby orienting the BINOL groups in a fashion potentially useful for molecular recognition of chiral substrates.

Fluorescent Recognition of 1,3-Diaminopropane in the Fluorous Phase – Greatly Enhanced Sensitivity and Selectivity

A 1,1′-binaphthyl-based dialdehyde, which is soluble in the fluorous phase, is synthesized. The fluorescence of this compound is greatly enhanced by 1,3-diaminopropane (DAP) in perfluorohexane (FC-72) but not by other amines and diamines. Thus, this compound can be used as a fluorescent sensor for the detection of the biologically important DAP at submicromolar concentrations. The selectivity and sensitivity of this fluorescent probe in this fluorous solvent are much greater than those in the common organic solvent dichloromethane.

Clarification of a misconception in the BINOL-based fluorescent sensors: Synthesis and study of major-groove BINOL-amino alcohols

The major-groove BINOL-amino alcohol (S)-6 shows greatly enhanced fluorescence over the minor-groove one (S)-3. The study of a series of the major-groove BINOL-amino alcohol compounds demonstrates that the commonly accepted acid inhibition of the PET fluo

Aminomethylation of BINOL with methyleneiminium salts

A new method for synthesizing chiral 3,3′-bis(N,N-dialkylaminomethyl) -1,1′-bi-2-naphthols with high enantiomeric excess is described. The procedure consists of bis-lithiation of diprotected (S)-or (R)-1,1′-bis(2- naphthol) followed by treatment of the intermediate with methyleneiminium salts. Mild reaction conditions prevent racemization and provide 3,3′-bis(N,N- dialkylaminomethyl)-1,1′-bi-2-naphthols or 3-(N,N-dialkylaminomethyl)-1, 1′-bi-2-naphthols with an enantiomeric excess >99%.

Synthesis and enantioselective fluorescent sensors for amino acid derivatives based on BINOL

Four novel derivatives of 1,1′-bi-2-naphthol have been prepared and the structures of these compounds characterised by IR, MS, 1H and 13C NMR spectroscopy and elemental analysis. The enantioselective recognition of these sensors has been studied by fluorescence titration and 1H NMR spectroscopy. The sensors exhibited different chiral recognition abilities towards N-Boc-protected amino acid anions and formed 1:1 complexes between the host and the guest. Sensors exhibit excellent enantioselective fluorescent recognition ability towards the amino acid derivatives.

Axially Chiral peri-Xanthenoxanthenes as a Circularly Polarized Luminophore

A series of axially chiral peri-xanthenoxanthenes (PXXs) were synthesized from 1,1′-bi-2-naphthol without optical resolution. These are the first examples of chiral PXXs. Among them, PXX 5 with two naphthalene rings connected via a methylenedioxy bridge and a chiral axis displayed intense fluorescence (FL) and circularly polarized luminescence (CPL) both in solution (φFL of 0.72 and |glum| of 1.4 × 10-3) and in the solid state (φFL of 0.13 and |glum| of 4.8 × 10-3). The bridged structure of PXX 5 adjusts the angle between the vectors of the electric and magnetic transition dipole moments, which is essential for showing intense CPL activity.

Photochemically reversible and thermally stable axially chiral diarylethene switches

A series of dithienylcyclopentenes containing axially chiral 1,1′-binaphthyl units were successfully synthesized by a Suzuki-Miyaura protocol. All these compounds exhibited photochemically reversible isomerization with thermal stability in both organic solvent and a liquid crystal (LC) host. When doping into an achiral LC host, some of them exhibited very high helical twisting powers. Reversible reflection wavelength tuning in the visible region and LC phase switching between nematic and cholesteric upon light irradiation were demonstrated.