Sodium, acetylide phenyl

Imagine that another reaction similar to that in Problem 9.81 is carried out between sodium acetylide and (R)-2-phenylpropana) to yield 1-phenyl-3-butyn-2-ol ... 

In order to explain the selectivity observed in cyclohexanones bearing polar substituents at position 4, Cieplak cited the reactions of 5-phenyl-2-adamantanone with sodium acetylide in liquid NH3 shown in Eq. 15 and 5-carbomethoxy-2-adamantanone with LiAl(0 Bu)3H in THF shown in Eq. 16. These reactions proceed with 66 34 and 83 17 selectivity in favor of axial attack. While the example in Eq. 15 may conform to the —> a overlap as indicated... 

Chlorine Ammonia, acetylene, alcohols, alkanes, benzene, butadiene, carbon disulflde, dibutyl phthalate, ethers, fluorine, glycerol, hydrocarbons, hydrogen, sodium carbide, flnely divided metals, metal acetylides and carbides, nitrogen compounds, nonmetals, nonmetal hydrides, phosphorus compounds, polychlorobi-phenyl, silicones, steel, sulfldes, synthetic rubber, turpentine... 

The first synthesis of a 3,5-diarylisoxazole from aryl hydroxamic acid chlorides and sodium phenyl acetylides was that effected by Weygand and Bauer in 1927. Beginning in 1946, when Quilico and Speroni showed that acid chlorides of hydroxamic acids on treatment with alkalies readily yielded nitrile oxides,numerous isoxazole and especially A -isoxazoline derivatives have been prepared. 

Acetyl chloride acephate, azaconazole, chlorfenvinphos, cyhalotrin, dimethomorph, dinoseb acetate, fenitropan, fluxofenim, furconazole, mefluidide, propiconazole Acetyl chloride (dichloro) see dichloro Acetyl chloride phenyl carbinol bromadiolone Acetylene aldrin, 2,4 DB Acetyl hydrazine metamitron Acetylide (sodium) pronamide Acetyl magnesiun bromide empenthrin Acetyl morpholine dimethomorph Acetyloxy propionaldehyde furmecyclox Acrolein 8 hydroxy quinoline sulfate Acrylic acid propaquizafop Acryloyl chloride propaquizafop Acrylonitrile fenpiclonil, fludioxonil, nipyraclofen Aldrin dieldrin, endrin... 

R-(R, S )]-p-Methyl-a-phenyl-1-pyrrolidineethanol is an important chiral mediator for the enantioselective addition of an acetylide to a prochiral ketone.2 3 This reaction has been successfully applied to the synthesis of the reverse transcriptase inhibitor efavirenz (DMP-266) (Scheme 1).3.4 Preparation of the enantiomer, (1S,2R)-N-pyrrolidinylnorephedrine, has been reported.2 The method used potassium carbonate (K2CO3) as base, but the yield of the product was only 33%. The submitters have extensively studied the formation of the pyrrolidinyl ring under various conditions as summarized in Table I. Eventually they found that the reaction was extremely efficient when it was run in toluene using sodium bicarbonate (NaHCC>3) as base (entry 8, Table I),5 which gave [R-(R, S )]-p-methyl-a-phenyl-1-pyrrolidineethanol quantitatively. Enantioselective (up to 99% ee) addition of cyclopropylacetylene to the ketoaniline 1 is achieved when the solution of [R-(R, S )]-p-methyl-a-phenyl-1-pyrrolidineethanol is used as a chiral additive.3 In addition, this method is also applicable to the preparation of a variety of alkylated norephedrines and other amino alcohols in excellent yields as Illustrated in Table II. These amino alcohols are potentially useful in asymmetric syntheses. 

---