Enantioselective synthesis of [1,1′-binaphthalene]-8,8′-diyl bis(diphenylphosphane) and its derivatives

Two 8,8′ disubstituted binaphthyl ligands have been designed and synthesized in 3.1% and 11.4% overall yield, respectively. X-ray structure analysis demonstrated that a unique chiral microenvironment was created. With the assistance of a new aggregation-induced polarization (AIP) technology, chiral aggregates were determined as the fraction of polar solvent increased in the nonpolar/polar solvent system, which indicated their potential in modern asymmetric synthesis and catalysis.


General Information
Unless otherwise stated, all reactions were magnetically stirred and conducted in oven-dried glassware in anhydrous solvents under Ar.Heated oil baths were used for reactions requiring elevated temperatures.Solvents were removed under reduced pressure at 40-65 °C using a rotavapor.All given yields are isolated yields of chromatographically and NMR spectroscopically materials.
The 1 H and 13 C NMR spectra were recorded in CDCl3 on 400 MHz and 100 MHz instruments with TMS as internal standard.For referencing of the 1 H NMR spectra, the residual solvent signal (δ = 7.26 for CDCl3) was used.In the case of the 13 C NMR spectra, the signal of solvents (δ = 77.06± 0.03 for CDCl3 and δ = 39.52 for DMSO-d6) were reported in ppm with respect to TMS.Data are represented as follows: chemical shift, multiplicity (s = singlet, d = doublet, t = triplet, m = multiplet), coupling constant (J, Hz), and integration.X-ray data were collected on a Rigaku XtaLAB Synergy-i Kappa diffractometer equipped with a PhotonJet-i X-ray source operated at 50 W (50kV, 1 mA) to generate Cu Kα radiation (λ = 1.54178Å) and a HyPix-6000HE HPC detector.Crystals were transferred from the vial and placed on a glass slide in polyisobutylene.A Zeiss Stemi 305 microscope was used to identify a suitable specimen for X-ray diffraction from a representative sample of the material.The crystal and a small amount of the oil were collected on a MiTeGen 100 micron cryoloop and transferred to the instrument where it was placed under a cold nitrogen stream (Oxford 700 series) at 100K.The sample was optically centered with the aid of a video camera to ensure that no translations were observed as the crystal was rotated through all positions.A unit cell collection was then carried out.After it was determined that the unit cell was not present in the CCDC database a data collection strategy was calculated by CrysAlis Pro1 .The crystal was measured for size, morphology, and color.

Synthesis of ±8
±7 (130 mg, 0.3 mmol), NaBH4 (114 mg, 3 mmol) and 15 mL methanol were added into a 50 mL round bottle flask.The flask was fitted with a balloon and stirred around 8 h.After completion of the reaction, the mixture was quenched by adding water.Then the solution was extracted with EA and washed by brine and water.The organic layer was concentrated by rotavapor and recrystallized in methanol to get crude product ±8. .
3.3 Syntheses of 3a and 3b 3a and 3b were synthesized from 2 following the reported procedure [2] with very minor modification.
3.5 Synthesis of 6a 4a (383 mg, 1 mmol), NBS (720 mg, 4 mmol) and 15mL CHCl3 were added in a 50 mL Schlenk flask.The flask was degassed under vacuum and backfilled with argon 3 times and then pyridine (0.24 mL, 3 mmol) was added.The mixture was stirred at 75 ℃ under argon overnight and quenched by 10 mL1M HCl.The reaction mixture was diluted with CH2Cl2 (30 mL) and washed with 20 mL brine.The organic phase was concentrated and purified by recrystallization with methanol, giving a brown solid 5a (0.27g, 50% yield).5a can be used without further purification.
HPLC conditions: Daicel Chrialpak IC column; hexane/2-propanol = 85/15, 1 mL/min, Retention times: 13.770 min (S), 39.543 min (R).5a (533 mg, 1 mmol) was dissolved in 10 mL dry THF in a Schlenk flask.The flask was degassed under vacuum and backfilled with argon 3 times.And then the mixture was stirred at -78℃ for 0.5 h and 2 mL1.6M n-BuLi was added drop wisely.20 mins later, Ph₂PCl (0.58 mL, 4 mmol) was added drop by drop.3 h later, the reaction was slowly warmed to room temperature and stirred overnight.After completion of the reaction, the mixture was extracted with DCM.The residue was dried by rotavapor and recrystallized by using methanol to give yellow solid 6a (300 mg, 40%

Synthesis of 7a
4 mL phosphorus oxychloride (POCl3) and 4 mL DMF were placed in a 50 mL round bottom flask, which was equipped with a rubber septum.The flask was put into an ice bath for 15 minutes with stirring, and 4a (766 mg, 2 mmol) dissolved in 6 mL CHCl3.The 4a solution was added into it drop by drop.The ice bath was removed, and the flask was equipped with an air condenser and heated to 75 o C for 12h, then cooled and poured into ice water.The pH of the mixture was changed to 7 by adding dilute KOH solution, and the precipitate was filtered to get crude product 7a (700 mg, 81%  with the aid of a video camera to insure that no translations were observed as the crystal was rotated through all positions.
A unit cell collection was then carried out.After it was determined that the unit cell was not present in the CCDC database a data collection strategy was calculated by CrysAlis Pro1 .The crystal was measured for size, morphology, and color.These values are reported in the accompanying Li21_10_auto_tables file.

Refinement Details
After data collection, the unit cell was re-determined using a subset of the full data collection.Intensity data were corrected for Lorentz, polarization, and background effects using the CrysAlis Pro1 .A numerical absorption correction was applied based on a Gaussian integration over a multifaceted crystal and followed by a semi-empirical correction for adsorption applied using the program SCALE3 ABSPACK 2 .The programs SHELXT 3 was used for the initial structure solution and SHELXL 4 was used for refinement of the structure.Both of these programs were utilized within the OLEX2 software 5 .Hydrogen atoms bound to carbon atoms were located in the difference Fourier map and were geometrically constrained using the appropriate AFIX commands. References: 1.
CrysAlis Pro (2018) Oxford Diffraction Ltd.It is advisable to attempt to resolve as many as possible of the alerts in all categories.Often the minor alerts point to easily fixed oversights, errors and omissions in your CIF or refinement strategy, so attention to these fine details can be worthwhile.In order to resolve some of the more serious problems it may be necessary to carry out additional measurements or structure refinements.However, the purpose of your study may justify the reported deviations and the more serious of these should normally be commented upon in the discussion or experimental section of a paper or in the "special_details" fields of the CIF.checkCIF was carefully designed to identify outliers and unusual parameters, but every test has its limitations and alerts that are not important in a particular case may appear.Conversely, the absence of alerts does not guarantee there are no aspects of the results needing attention.It is up to the individual to critically assess their own results and, if necessary, seek expert advice.

Publication of your CIF in IUCr journals
A basic structural check has been run on your CIF.These basic checks will be run on all CIFs submitted for publication in IUCr journals (Acta Crystallographica, Journal of Applied Crystallography, Journal of Synchrotron Radiation); however, if you intend to submit to Acta Crystallographica Section C or E or IUCrData, you should make sure that full publication checks are run on the final version of your CIF prior to submission.

Publication of your CIF in other journals
Please refer to the Notes for Authors of the relevant journal for any special instructions relating to CIF submission.It is advisable to attempt to resolve as many as possible of the alerts in all categories.Often the minor alerts point to easily fixed oversights, errors and omissions in your CIF or refinement strategy, so attention to these fine details can be worthwhile.In order to resolve some of the more serious problems it may be necessary to carry out additional measurements or structure refinements.However, the purpose of your study may justify the reported deviations and the more serious of these should normally be commented upon in the discussion or experimental section of a paper or in the "special_details" fields of the CIF.checkCIF was carefully designed to identify outliers and unusual parameters, but every test has its limitations and alerts that are not important in a particular case may appear.Conversely, the absence of alerts does not guarantee there are no aspects of the results needing attention.It is up to the individual to critically assess their own results and, if necessary, seek expert advice.

Publication of your CIF in IUCr journals
A basic structural check has been run on your CIF.These basic checks will be run on all CIFs submitted for publication in IUCr journals (Acta Crystallographica, Journal of Applied Crystallography, Journal of Synchrotron Radiation); however, if you intend to submit to Acta Crystallographica Section C or E or IUCrData, you should make sure that full publication checks are run on the final version of your CIF prior to submission.

Publication of your CIF in other journals
Please refer to the Notes for Authors of the relevant journal for any special instructions relating to CIF submission.
mixture was quenched by adding water.Then the solution was extracted with EA and washed by brine and water.The organic layer was concentrated by rotavapor and recrystallized in methanol to get whit solid 8a (117 mg, 90%).HRMS (ESI-TOF) m/z [C26H26O6 +Na] 3.7 Synthesis of 8a 7a (130 mg, 0.3 mmol), NaBH4 (114 mg, 3 mmol) and 15 mL methanol were added into a 50 mL round bottle flask.The flask was fitted with a balloon and stirred around 8 h.After completion of the reaction, the