Poly(1,1‘-bi-2-naphthol)s:  Synthesis, Characterization, and Application in Lewis Acid Catalysis

Abstract

6,6‘-Dibromo-1,1‘-bi-2-naphthol derivatives, where the hydroxyl groups are protected by alkyl, methoxymethyl, and acyl groups, have been polymerized using nickel(0) or nickel(II) complexes as catalysts. The molecular weights of the resulting polymers have been analyzed by gel permeation chromatography and laser light scattering. Hydrolysis of these polymers has produced the optically active poly(1,1‘-bi-2-naphthol)s [poly(BINOL)s]. The poly(BINOL)s are soluble in basic water solution and have been characterized by NMR, IR, UV, and CD spectroscopic methods. The reaction of a (R)-poly(BINOL) with diethylaluminum chloride, trimethylaluminum, and titanium tetraisopropoxide generates novel polymeric Lewis acid complexes. These complexes represent a new generation of polymeric catalysts where the catalytic centers are highly organized in an optically active and sterically regular polymer chain. When used to catalyze the Mukaiyama aldol condensation, the polymeric aluminum catalyst shows greatly enhanced catalytic activity over the monomeric complex.

Synthesis of chiral conjugated propeller-like polymers using optically active 1,1′-binaphthyl-2,2′-diamine derivatives

“…Applications of these compounds in asymmetric synthesis and chiral recognition have been extensively studied [1][2][3] . Recently, we have also used the optically active 1 as the starting material to build a class of chiral conjugated polymers for materials application [4][5][6][7][8][9][10] as well as for asymmetric catalysis [11][12][13][14][15] . Among these materials, (R)-2 represents a structurally very interesting polymer ( Fig.…”

Synthesis and properties of chiral helical chromophore-functionalised polybinaphthalenes for second-order nonlinear optical applications

“…The polymer backbone consists of chiral binaphthalene unit, connected with rigid groups, to ensure the chiral, helical conformation [6][7]10]. Hexyl groups were incorporated for solubility reasons and the chromophores were linked to the polymer backbone through the naphthol functions.…”

“…Hexyl groups were incorporated for solubility reasons and the chromophores were linked to the polymer backbone through the naphthol functions. The precursor polymers were prepared by means of a Suzuki reaction, because this pathway yields the highest molecular weights [7]. Direct polymerisation of chromophore-functionalised monomers to obtain chromophore-functionalised polymers, is not possible under this conditions, since this would lead to chromophore degradation.…”

“…The organic layer was washed with a saturated NaHCO 3 -solution and brine and dried over Fig. 2 ppol I was synthesized according to literature procedure [6], by reaction of 3a [7] and 4 [6]. …”

Rigid and Sterically Regular Chiral 1,1′-Binaphthyl Polymers in Asymmetric Catalysis

“…[10,11] It is synthesized from the Ni 0 or Ni II /Zn mediated polymerization of 6,6'-dibromo binaphthyl monomers (R)-3 followed by hydrolysis (Scheme 1). Polymer (R)-4 is soluble in benzyl alcohol, DMF, and basic aqueous solution, but insoluble in methylene chloride, chloroform, benzene, toluene, and THF.…”