Chiral linear polymers bonded alternatively with salen and 1,4-dialkoxybenzene: synthesis and application for Ti-catalyzed asymmetric TMSCN addition to aldehydes

The synthesis of chiral linear polymers 1a–b having salen and 1,4-dioctyloxybenzene as alternate segments has been accomplished. The GPC analysis showed the molecular weights corresponding to ca. 15 (Mw = 10,999, Mn = 9165 and PDI = 1.20) repeating units for 1a and ca. 8 (Mw = 8547, Mn = 7883 and PDI = 1.08) repeating units for 1b. Polymers 1a–b have been studied with Ti(OiPr)4 as a recyclable catalyst for the asymmetric addition of TMSCN to aldehydes while the selectivity of the polymer catalyst is identical to that of the monomer. The reactions are efficient affording the cyanohydrins with up to 88% ee. The selectivity of the polymer based catalyst 9a is found to be the same to that of the monomer 10a. The reaction provides the advantages of simplified product isolation and easy recovery and recyclability of polymer catalyst 9a without any loss of activity or selectivity.

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Polymer 1aMonomeric unit: C50H72N2O4[α]D20=+231 (c 0.026, CHCl3)Mw = 10,999, Mn = 9165, PDI = 1.20Source of chirality: (1R,2R)-(−)-1,2-diaminocyclohexaneAbsolute configuration: (R,R)

Polymer 1bMonomeric unit: C58H74N2O4[α]D20=+95 (c 0.021, CHCl3)Mw = 8547, Mn = 7883, PDI = 1.08Source of chirality: (1R,2R)-(+)-1,2-diphenylethylenediamineAbsolute configuration: (R,R)

(+)-2-Hydroxy-2-(2′-bromophenyl)acetonitrileC8H6NOBr[α]D20=+6.3 (c 1.09, CHCl3)Ee = 50%Source of chirality: chiral polymer catalyst 9aAbsolute configuration: n.d.

(2S)-(+)-Hydroxy-2-(2′-chlorophenyl)acetonitrileC8H6NOCl[α]D20=+1.6 (c 0.43, CHCl3)Ee = 60%Source of chirality: chiral polymer catalyst 9aAbsolute configuration: (S)

(2S)-(−)-Hydroxy-2-(2′-methoxyphenyl)acetonitrileC9H9NO2[α]D20=-23.9 (c 0.37, CHCl3)Ee = 88%Source of chirality: chiral polymer catalyst 9aAbsolute configuration: (S)

(−)-2-Hydroxy-2-(2′-ethoxyphenyl)acetonitrileC10H11NO2[α]D20=-38.0 (c 0.61, CHCl3)Ee = 78%Source of chirality: chiral polymer catalyst 9aAbsolute configuration: n.d.

(+)-2-Hydroxy-2-(2′-allyloxyphenyl)acetonitrileC11H11NO2[α]D20=+22.5 (c 0.75, CHCl3)Ee = 75%Source of chirality: chiral polymer catalyst 9aAbsolute configuration: n.d.

(−)-2-Hydroxy-2-(3′-bromophenyl)acetonitrileC8H6BrNO[α]D20=-19.5 (c 1.34, CHCl3)Ee = 75%Source of chirality: chiral polymer catalyst 9aAbsolute configuration: n.d.

(2S)-(−)-Hydroxy-2-(4′-methoxyphenyl)acetonitrileC9H9NO2[α]D20=-32.4 (c 0.55, CHCl3)Ee = 78%Source of chirality: chiral polymer catalyst 9aAbsolute configuration: (S)

(2S)-(−)-Hydroxy-2-(4′-methylphenyl)acetonitrileC9H9NO[α]D20=-31.5 (c 0.51, CHCl3)Ee = 68%Source of chirality: chiral polymer catalyst 9aAbsolute configuration: (S)

(2S)-(−)-Hydroxy-2-(2′-naphthyl)acetonitrileC12H9NO[α]D20=-24.6 (c 1.16, CHCl3)Ee = 74%Source of chirality: chiral polymer catalyst 9aAbsolute configuration: (S)

(−)-2-HydroxybutanenitrileC4H7NO[α]D20=-10.3 (c 0.89, CHCl3)Ee = 40%Source of chirality: chiral polymer catalyst 9aAbsolute configuration: n.d.

(2S)-(−)-Hydroxy-3-methylbutanenitrileC5H9NO[α]D20=-10.5 (c 1.19, CHCl3)Ee = 66%Source of chirality: chiral polymer catalyst 9aAbsolute configuration: (S)

(E)-(2S)-(+)-Hydroxypent-3-enenitrileC5H7NO[α]D20=+10.5 (c 0.50, CHCl3)Ee = 55%Source of chirality: chiral polymer catalyst 9aAbsolute configuration: (S)