The Development of Organic Reactions with Metallic Samarium.

• Yanada Reiko

  Department of Organic Chemistry, Graduate School of Pharmaceutical Sciences, Kyoto University

• Ibuka Toshiro

  Department of Organic Chemistry, Graduate School of Pharmaceutical Sciences, Kyoto University

Bibliographic Information

Other Title

• 金属サマリウムを利用する合成反応の開発
• キンゾク サマリウム オ リヨウ スル ゴウセイ ハンノウ ノ カイハツ

Abstract

The chemistry of metallic samarium (Sm) is of current interest in organic synthesis. Though samarium iodide (SmI₂) is a good synthetic tool (a mild, neutral and ether-soluble one-electron reductant), its sensitivity to air makes it rather difficult to handle. We have been studying the reactivity of Sm to overcome this drawback of SmI₂. Dehalogenation of vic-dihalides with Sm gave alkenes and alkynes. These reductions were accelerated with a catalytic amount of acid. Olefinic double bonds of various α, β-unsaturated carboxylic acid derivatives (ester, amide, nitrile, carboxylic acid) were also reduced to give the corresponding 1, 4-reduction products. Aromatic carbonyl compounds were reduced to the corresponding pinacol coupling products with Sm-I₂ or Sm-I₂-Ti (OⁱPr) ₄ in methanol. Meso isomers were mainly produced in the presence of Ti (OⁱPr)₄ Acyl- or alkoxycarbonyl-protected alcohols or amides are deprotected easily and selectively under mild and neutral conditions. Stereoselective allylation and dimerization of optically active imines with Sm and a catalytic amount of I₂ have been successfully accomplished. Both Barbier-type allylation and intermolecular pinacol-like coupling reaction of imines were carried out smoothly to give allylation products and C₂-2, 2'-ethylenediiminodiethanol derivatives in a highly diastereoselective manner. This novel C₂-dimeric amino alcohols bearing primary alcohols catalyzed enantioselective addition of diethylzinc to aldehydes.

Journal

• Journal of Synthetic Organic Chemistry, Japan

  Journal of Synthetic Organic Chemistry, Japan 58 (6), 597-605, 2000

  The Society of Synthetic Organic Chemistry, Japan

Keywords

• metallic samarium
• reductive dehalogenation
• 1, 4-reduction
• pinacol coupling
• deprotection
• diastereoselective allylation of imines
• diastereoselective coupling of imines
• C<SUB>2</SUB>-chiral ligand
• diethylzinc
• enantioselective addition

Details

• CRID: 1390282680253566976
• NII Article ID: 10008820478
• NII Book ID: AN0024521X
• DOI: 10.5059/yukigoseikyokaishi.58.597
• COI: 1:CAS:528:DC%2BD3cXktVaitL0%3D
• ISSN: 18836526
• ISSN: 00379980
• NDL BIB ID: 5365316
• Web Site: https://ndlsearch.ndl.go.jp/books/R000000004-I5365316
• Text Lang: ja
• Data Source:
  • JaLC
  • NDL
  • Crossref
  • CiNii Articles
• Abstract License Flag: Disallowed