A Novel Synthetic Methods Through Alpha, Beta-Epoxy Sulfoxides and Related Compounds

α、β-环氧亚砜及相关化合物的新合成方法

• 批准号: 01571168
• 负责人: SATOH Tsuyoshi
• 金额: $ 1.02万
• 依托单位: Science University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1989
• 资助国家: 日本
• 起止时间: 1989 至 1990
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-01571168/
• 关键词: alpha, beta-Epoxy sulfoxide; Methylenecyclopropane; 3-Methylfuran; alpha-Hydroxy acid alcohol; Asymmetric synthesis; Propargylic; alpha-Halo ketone; Chlorooxylane; ノ-クロロアリルスルホキシド; 3ーXチルフラン; αーヒドロチシカルボン酸; 1-クロロアルキルアリルスルホキシシド; α,β-エポキシスルホキシド; α

A novel methods are developed from the addition of 1-chloroalkyl aryl sulfoxides with carbonyl compounds through the chloroalcohols and alpha, beta-epoxy sulfoxides. Treatment of the alpha, beta-epoxy sulfoxides with LiClO_4 gave alpha, beta-unsaturated ketones, which were converted to allylic epoxides in three steps in good overall yields. These allylic epoxides were treated with LDA to afford spiro-linked methylenecyclopropanes in high yields. These methylenecycopropanes were then converted to fused 3-methylfurans. Thermal elimination of the chloroalcohols gave vinyl chlorides in quantitative yields, which were oxidized with ozone to afford alpha-hydroxycarboxylic acids and their derivatives in good yields. This method was developed to an asymmetric synthesis of them using optically active 1-chlorobutyl p-tolyl sulfoxide. Epoxydation of the vinyl chlorides gave chlorooxylanes, Which were reacted with various nucleophiles to afford alpha-hydroxy alpha'-substituted ketones in good yields. Treatment of the vinyl chlorides with excess n-BuLi afforded propargylic alcohols and acetylene diols in high overall yields. Swern oxidation of the above mentioned chloroalcohols gave alpha-halo alpha-alkyl beta-keto sulfoxides. These were treated with EtMgBr to give alpha-halo ketones in quite high yields.

通过氯代醇和α，β-环氧亚砜与羰基化合物的加成反应，开发了一种新的方法。α，β-环氧亚砜与LiClO_4反应生成α，β-不饱和酮，经三步反应得到烯丙基环氧化物，总收率较高。用LDA处理这些烯丙基环氧化物，以高产率得到螺环连接的亚甲基环丙烷。然后将这些亚甲基呋喃丙烷转化为稠合的3-甲基呋喃。热消除氯醇得到定量产率的氯乙烯，用臭氧氧化得到高产率的α-羟基羧酸及其衍生物。将此方法发展到用光学活性的1-氯丁基对甲苯基亚砜不对称合成它们。氯乙烯环氧化得到氯代十四烷，再与各种亲核试剂反应，以较好的产率得到α-羟基α ′-取代酮。用过量的n-BuLi处理氯乙烯，以高的总收率得到炔丙醇和炔二醇。上述氯代醇的Swern氧化得到α-卤代α-烷基β-酮基亚砜。这些用EtMgBr处理，以相当高的产率得到α-卤代酮。

项目成果

T. Satoh, J. Shishikura, and K. Yamakawa: "Ring-opening Fluorination of alpha, beta-Epoxy Sulfoxides : A Novel Synthesis of alpha-FluoroKetones" Chem. Pharm. Bull.38. 1798 (1990)

T. Satoh、J. Shishikura 和 K. Yamakawa：“α，β-环氧亚砜的开环氟化：α-氟酮的新型合成” Chem。

Tsuyoshi Satoh: "Nucleophilic RingーOpening of Chlorooxiranes: A New Synthesis of αーHydroxy α′ーsubstituted Ketones from Carbonyl Compounds and 1ーChloroalkyl pーTolyl Sulfoxides" Bull.Chem.Soc.Jpn.,. 64. (1991)

Tsuyoshi Satoh：“氯环氧乙烷的亲核开环：从羰基化合物和 1-氯烷基对甲苯亚砜中合成 α-羟基 α-取代酮”Bull.Chem.Soc.Jpn. 64。 (1991)

T. Satoh, T. Fujii, and K. Yamakawa: "A New Synthesis of beta-Keto Sulfoxides from Chloromethyl Aryl Sulfoxide and Aldehydes" Bull. Chem. Soc. Jpn.63. 1266 (1990)

T. Satoh、T. Fujii 和 K. Yamakawa：“从氯甲基芳基亚砜和醛中合成 β-酮亚砜”公牛。

Tsuyoshi Satoh: "A Novel Synthesis of Carbocyclic SpiroーType Methylenecyclopropane Derivatives" Tetrahedron Lett.,. 31. 3609-3610 (1990)

Tsuyoshi Satoh：“碳环螺型亚甲基环丙烷衍生物的新合成”Tetrahedron Lett., 31. 3609-3610 (1990)

Tsuyoshi Satoh: "A Novel Synthesis of Both Enantiomers of αーHydroxycarboxylic Esters and Amides from (ー)ー1ーChlorobutyl pーTolyl Sulfoxide" Tetrahedron Lett.,. 31. 3567-3570 (1990)

Tsuyoshi Satoh：“从 (-)-1-氯丁基对甲基亚砜合成 α-羟基羧酸酯和酰胺的两种对映体”Tetrahedron Lett., 31. 3567-3570 (1990)