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en: The Barbier-Type Alkylation of Carbonyl Compounds with Alkyl Iodides Using Metallic Strontium --- 簡便な第3級アルコール製造法

ja: 金属ストロンチウムを用いるBarbier型アルキル化反応の開発 --- 簡便な第3級アルコール製造法

en: Fine chemicals

ja: ファインケミカル


en: The Barbier-Type Alkylation of Carbonyl Compounds with Alkyl Halides Using Metallic Strontium

ja: 金属ストロンチウムを用いるBarbier型アルキル化反応の開発

en: Organometallic compounds comprise some of the most versatile reagents in organic synthesis, and among them are organometallic compounds of alkaline-earth elements. Numerous reports have been published on the Grignard (or Barbier) reaction using metallic magnesium and alkyl halides. Furthermore, there are various reports on the preparation and reactivity of the organometallic compounds of calcium and barium. In contrast, fewer studies on the preparation and reactivity of organostrontium compounds were found in the literature. As the results on our investigation, it's found that in the presence of metallic strontium, the Barbier-type alkylation of aldehydes with alkyl iodides proceeded smoothly at-15°C under an argon atmosphere to afford the corresponding alkylated alcohols in moderate to good yields. The Barbier-type alkylation of imines with alkyl iodides also took place smoothly at room temperature under an argon atmosphere to give the corresponding alkylated amines in good yields. Aromatic aldimines reacted with metallic strontium in the presence of a catalytic amount of iodine to obtain the self-coupling products in good yields. Furthermore, the Barbier-type alkylation of esters with alkyl iodides proceeded smoothly at room temperature under an argon atmosphere to afford the corresponding dialkylated alcohols in good yields.

en: Journal of Synthetic Organic Chemistry, Japan

ja: 有機合成化学協会誌


en: Organic Synthesis by Using Bismuth and Tin Compounds: Synthetic Organic Reaction in Aqueous Media

ja: ビスマスやスズ化合物を用いる有機合成―含水溶媒中や水中での有機合成反応を中心にして―

en: A review with 36 refs. on (1) Grignard-type addn. of allyl unit to carbonyl compds. contg. CO2H by using BiCl3-Zn-allyl bromide, (2) allylation of aldehydes by using allylic alcs. in the presence of Bi, (3) a novel aq. Barbier-Grignard-type allylation of aldehydes in a Mg/BiCl3 bimetal system, (4) allylation of carbonyl compds. by using allyl Grignard reagent and various metallic salts in aq. media, (5) allylation of aldehydes by using allyltin compds. in aq. media, (6) asym. allylation of carbonyl compds. by using tetraallyltin, (7) Bi-mediated allylation of unprotected carbohydrates, (8) ether synthesis by using a catalytic amt. of BiCl3 and Et3SiH, (9) asym. cyanation of aldehydes promoted by a catalytic amt. of chiral Bi compd., and (10) redn. of aldehydes by using Bu3SnH in MeOH or H2O.