Sequential Knoevenagel Reaction/Mislow-Evans Rearrangement Catalyzed by Heterogeneous Amine Grafted on Silica in Water, Leading to γ-Hydroxy-α,β-unsaturated Nitrile

Abstract

γ-Hydroxy-α,β-unsaturated nitrile was obtained by the reaction of α-arylsulfinylacetonitrile with aldehyde in water, which was catalyzed by N,N-diethylaminopropylated silica gel. The overall transformation proceeded via five sequential reactions, 1,2-addition of acetonitrile, dehydration (Knoevenagel condensation), isomerization of the double bond, rearrangement of sulfinyl group (Mislow-Evans rearrangement) and hydrolysis of sulfinyl ester. The reaction condition was mild such that the AcO, TBMDSO or OTHP group remained intact in the products.

Key words

green chemistry - aqueous reaction - condensation - re­arrangement - supported catalysis - sulfoxides

References and Notes

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10

Typical Experimental Procedure.
To a suspension of NDEAP (168 mg, 0.17 mmol, amine loading 0.99 mmol/g) in H₂O (1 mL) was added m-chloro-phenylacetonitrile (102 mg, 0.52 mmol) under nitrogen atmosphere. After being stirred for 10 min, (+)-citronellal (63 µL, 0.35 mmol) was added and stirring was continued for 6 h at r.t. After addition of 10% aq Et₂NH (30 µL, 0.029 mmol), the mixture was stirred for 10 min. Product was triturated with EtOAc four times under vigorous stirring. The combined organic layer was evaporated to dryness and the residue was purified by medium pressure LC (eluent: EtOAc-n-hexane = 1:2) to give a diastereomeric mixture of (2E)-4-hydroxy-5,9-dimethyldeca-2,8-dienenitrile (54 mg, 80%).