Enantioselective Fluorescent Recognition of Amino Alcohols by a Chiral Tetrahydroxyl 1,1‘-Binaphthyl Compound

Abstract

The tetrahydroxyl derivative of BINOL, (S)-or (R)-1, and its analogs are synthesized. (S)-or (R)-1 can be used to conduct the enantioselective recognition of chiral amino alcohols. In comparison with BINOL, the two additional hydroxyl groups of (S)-or (R)-1 have increased the binding of this compound with the amino alcohols and significantly improved the fluorescence quenching efficiency. The fluorescence responses of (S)-or (R)-1 towards amino alcohols are compared with those of its analogs (R)-4 and (R)-6. It shows that the interaction of the central naphthyl hydroxyl groups of (S)-or (R)-1 with the substrates is responsible for the observed fluorescence quenching and the two additional alkyl hydroxyl groups increase the quenching efficiency.

Desymmetrization of Prochiral Diaryl Sulfoxides by an Asymmetric Sulfoxide–Magnesium Exchange

“…Using iPrMgBr·LiCl and Li 2 -12 instead of iPr 2 Mg and Li 2 -12 caused yield (31 %) and enantioselectivity (27 % ee) losses (Table 1, entry 7). When the bulkier BINOL derivative 13 [29] was deprotonated instead of 12 to become the chiral auxiliary the enantiocontrol almost vanished (89 % yield, 3 % ee; (Table 2, entry 5)] we optimized 1) the exchange temperature T 1 , 2) the ligand/substrate ratio, and 3) the solvent-to the extent summarized in Table 2. The resulting sulfoxide 9 c was uniformly levorotatory.…”

Synthesis, Characterization and Application of Some Axially Chiral Binaphthyl Phosphoric Acids in Asymmetric Mannich Reaction

“…The intermediate 2a [37,38] was obtained by reacting (R)-BINOL with diphenylphosphoric chloride in the presence of sodium hydride and subsequent LDA induced rearrangement of the intermediate 1a at low temperature to afford the desired 3,3'-disubstituted axially chiral 1,1'-binaphthalene-2,2'-diol. On the other hand, 2b [35] and 2c [36] were generated through methoxymethyl (MOM) protected BINOL. Quinoline was introduced at 3,3' positions of (R)-2,2'-bis(methoxymethoxy)-1,1'-binaphthalene (1e) in the presence of butyl lithium at -40 ℃ and then the product was refluxed in nitrobenzene to afford 1b.…”

“…After deprotection of 1b and 1c under acidic conditions, 3,3'-(disubstituted) BINOLs were produced. Furthermore, another useful substituted BI-NOL 2d [36] could be obtained from the intermediate 2c by selective protection of more active hydroxyl groups by methanol in the presence of strong acid CF 3 COOH. Having prepared the substituted BINOLs 2a-2d as potent precursors to chiral phosphoric acids, we turned our attention to convert them into the Brønsted acids 3a -3d.…”

A BINOL Based Fluorescence Sensor for Distinction of D‐Glucose

“…[20][21][22][23][24][25][26][27] Our group has developed a series of fluorescence receptors based on 1,1'-binaphthol for recognitions of anions, cations, and amino acids. [28][29][30][31][32][33] The BINOL molecule has the following characteristics: (1) a stable chiral configuration with both enantiomers, Rand S-BINOL, commercially available; (2) a highly tunable structure of the BINOL molecule since functional groups can be specifically introduced to the 2-, 3-, 4-, 5-and 6-positions; (3) a good fluorescence properties systematically varied by structural modification. [34] The first case of chiral sensing for monosaccharides was based on 1,1'-BINOL reported by James.…”