Efficient resolution of 2,2′-dihydroxy-1,1′-binaphthyl by inclusion complexation with chiral N-(3-chloro-2-hydroxypropyl)-N,N,N-trimethylammonium chloride

Abstract

The complete resolution of 2,2[prime or minute]-dihydroxy-1,1[prime or minute]-binaphthyl into its enantiomers by inclusion complexation with a commercially available derivative of choline, is reported. The two enantiomers are recovered in >99% ee from the inclusion complexes by simple dissolution in a diethyl ether-water medium and the resolving agent can be recycled.

Control of Differential Inclusion Complexation in the Solid State by Seed Crystals

“…Crystal data for 1·(Et 2 O) 2 (2): C 28 H 34 O 4 , M r = 434.55, monoclinic, b = 108.86(2)8, a = 11.659(7), b = 9.757(6), c = 11.886(7) , V = 1279.4(13) 3 , T = 293 K, space group Pn, Z = 2, l(Cu Ka ) = 1.54 ; for 1835 observed reflections, the final R (on F) = 0.0798 and wR (on . Keywords: crystal growth · host-guest systems · inclusion compounds · solid-state reactions…”

“…When the complexation was performed slowly from a diluted solution, the less stable 2 (1·(Et 2 O) 2 ) crystallized out. This is the first example of differential inclusion complexation by controlling the concentration of the solution, although differential complexations by controlling the temperature [3] or the type of solvent used for crystallization [4] have also been reported. However, when 1 (0.2 g) was recrystallized from an intermediate volume of Et 2 O (4 mL), either 2 or 3 formed [a] The ratio was determined by 1 H NMR spectroscopy and thermogravimetric analysis.…”

“…As optically active 1 precisely recognizes the chirality of the guest molecule it includes, enantiomeric separation of the guest can be performed easily. [3] However, inclusion complexation of guest compounds with racemic 1 has not been extensively studied to date. Herein, we report that differential inclusion complexation between racemic host 1 and simple gaseous guests in the solid state can be controlled by a seed crystal.…”

An economic, practical access to enantiopure 1,1′-bi-2-naphthols: enantioselective complexation of threo-(1S,2S)-N-benzyl-N,N-dimethyl[1,3-dihydroxy-1-(4′-nitrophenyl)]-2-propylammonium chloride

“…1,2 To meet this progressive need, a large number of preparative methods for enantiopure (S)-and (R)-BI-NOL have been reported, including fractional crystallization of diastereoisomers, 3,4 resolution with enzymes or microorganisms, 5 asymmetric oxidation coupling, 6 and enantioselective complexation. [7][8][9][10][11][12][13] As far as the complexation method is concerned, N-benzylcinchonidinium chloride, 7 N-benzylcinchonidinium chloride, 8 (S)-5-oxopyrrolidine-2-carboxanilide, 9 (S,S)-1,2-diaminocyclohexane, 10 chiral sulfoxide 11 N-(3-chloro-2-hydroxy-propyl)-N,N,Ntrimethylammonium chloride, 12 and ethers of tartaric acid derivatives 13 have been used as chiral complexing agents.…”

Optical resolutions by inclusion complexation with a chiral host compound

“…The other one is that complex of 14b or 14c with 155 is easily dissociated into the components by treatment with ether-water mixture to give an ether solution of 14b or 14c and an aqueous solution of 155. 69 …”