G. Courtois

Addition d'organometalliques allyliques et d'organolithiens satures aux enynes conjugues, simples et fonctionnels

Abstract Reactive organometallic compounds such as allyl-zinc, -magnesium, and -lithium and saturated lithium compounds are shown to bring about readily an addition reaction with simple and α-substituted conjugated enynes RCCCHCHCH2 R′ [R = H, CH3;R′ = alkyl, OH, OC4H9, NHC2H5, N(C2H5)2]. The regioselectivity of the reaction depends on the nature of the metal atom in the organometallic compound. The reaction takes place also in certain cases with organometallic vinyl compounds.

Synthese univoque d'amines tertiaires insaturees par voie organometallique a partir de gem-aminoethers

Abstract In this work, the best methods for preparing unequivocally and in good yields β-acetylenic, α-allenic and β-ethylenic tertiary amines have been evaluated.

Addition du di-t-butyl-zinc a la triple liaison des enynes conjugues, simples et fonctionnels

Abstract Di-t-butylzinc adds easily to conjugated enynes . Only the acetylenic bond is involved in this reaction which proceeds via trans -addition. This regioselective and stereoselective addition leads to conjugated dienes .

Etude du comportement d'organometalliques (M = Zn, Mg, Li) vis a vis d'enynes conjugues : II. Cas des enynes fonctionnels: HCCC(R)C(R′)(CH2)nR″; Influence de la structure sur la reactivite et la regioselectivite☆

Reactive organometallic compounds such as allyl-zinc, -magnesium,-lithium and saturated lithium compounds are shown to readily undergo addition reactions with functionally conjugated enynes: HCCC(R)C(R′)(CH2)nR″ (R″ = OH, OC4H9, NHC2H5N(C2H5)2), but the reactivity is reduced when the steric hindrance around the double bond is increased. With each organometallic compound used, this reaction is regioselective: 3,4 addition with organozinc compounds, 1,2 addition with organolithium compounds (allyl-, butyl-) and both 1,2 and 1,4 addition with organomagnesium compounds.

Addition regioselective d'organometalliques α-insatures ou α-fonctionnels au chlorure de n-ethoxycarbonylpyridinium : synthese de dihydro-1,2 (ou -1,4) pyridines 2-(ou 4-)substituees.

Abstract α-unsaturated and α-functional organometallics easily react with 1-ethoxycarbonylpyridinium chloride to lead to 1,2 (or 1,4) substituted dihydropyridines. From these dihydropyridines, either pyridines or piperidines can be prepared.

Etude de la régiosélectivité de l'action des organozinciques sur les α-iminoesters: synthèse d'α-aminoesters C-substitués par un groupe α-insaturé ou α-fonctionnel

Abstract Organozinc compounds prepared from allylic or propargylic bromides, and from α-bromoesters or α-bromoamides react regiospecifically with α-iminoesters R′NCHCOOR″ (R′,R″ = primary, secondary or tertiary alkyl group) to give α-aminoesters R′NHCH(R)COOR″ in good yields.

Synthese univoque d'amines tertiaires insaturees par voie organometallique a partir de sels d'immonium : I. Synthese d'amines β-acetyleniques, α-acetyleniques et α-alleniques

Abstract The best method to prepare unequivocally and in good yields β-acetylenic, α-acetylenic and α-allenic tertiary amines RR′CHNR″ 2 (R unsaturated group, R′, R″ alkyl groups) from immonium salts has been evaluated.

Étude de la synthése, la structure et la réactivité d'un nouveau réactif organométallique résultant d'une réaction de dimérisation du bromure d'allyl-zinc

Abstract When heated for several hours in refluxing solvent, allylzinc bromide forms a new organometallic compound with a bis-1,3-organozinc structure. This compound reacts with different compounds leading in most cases to attachment of the structural group:

Synthèse en une étape par voie organométallique d'amines primaries β-acétyléniques α-ramifiées

Abstract The one-pot synthesis of α-branched β-alcynyl primary amines results from reaction between organometallic compounds, prepared from propargylic bromides and N-silylimines derived from aromatic or aliphatic aldehydes. Usually, the reaction is regioselective, but not in the case of CH3CCCH2M.

Synthese univoque d'amines tertiaires insaturees par voie organometallique a partir de sels d'immonium : II. Synthese d'amines β- et α-ethyleniques

In this work, the best method to prepare unequivocally and in good yields β-and α-ethylenic tertiary amines: RR′CHNR″2 (R unsaturated group, R′, R″ alkyl groups), from immonium salts, has been evaluated.