Ethyl reaction with cinnamyl chloride

A solution of ( )-cinnamyl alcohol (0.523 g, 4 mmol) in dry cumene (3mL) was added dropwise over a period of 0.5 h at — 10°C to a solution of n-BuLi/hexane (7.5 mL, 12 mmol) in the presence of (—)sparteine (0.92 mL, 4 mmol) in dry cumene (5mL). The red reaction mixture was stirred at 0 °C for 1 h. After cooling, the reaction mixture was poured into IMHCl. The aqueous layer was extracted with ether (2 X lOmL), and the combined organic phases were dried over MgS04. After evaporation of the solvent, the residue was chromatographed on silica gel (eluent 80 20 cyclohexane/ethyl acetate). Yield of (S)-93, 82% (0.632 g) 0 - = — 4.1° (c = 0.175, methylene chloride). 

Cuprous chloride tends to form water-soluble complexes with lower olefins and acts as an IPTC catalyst, e.g., in the two-phase hydrolysis of alkyl chlorides to alcohols with sodium carboxylate solution [10,151] and in the Prins reactions between 1-alkenes and aqueous formaldehyde in the presence of HCl to form 1,3-glycols [10]. Similarly, water-soluble rhodium-based catalysts (4-diphenylphosphinobenzoic acid and tri-Cs-io-alkylmethylam-monium chlorides) were used as IPTC catalysts for the hydroformylation of hexene, dodecene, and hexadecene to produce aldehydes for the fine chemicals market [152]. Palladium diphenyl(potassium sulfonatobenzyl)phosphine and its oxide complexes catalyzed the IPTC dehalogenation reactions of allyl and benzyl halides [153]. Allylic substrates such as cinnamyl ethyl carbonate and nucleophiles such as ethyl acetoactate and acetyl acetone catalyzed by a water-soluble bis(dibenzylideneacetone)palladium or palladium complex of sulfonated triphenylphosphine gave regio- and stereo-specific alkylation products in quantitative yields [154]. Ito et al. used a self-assembled nanocage as an IPTC catalyst for the Wacker oxidation of styrene catalyzed by (en)Pd(N03) [155]. 

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