diketene

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧杂环丁烷
• 英文名称: diketene
• 英文别名: Diketen；2-Methyleneoxetan-3-one；2-methylideneoxetan-3-one
• 化学式: C₄H₄O₂
• 分子量: 84.0746
• InChiKey: KPVUQTCGODHFLR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  6
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-甲基炔丙基胺 、 diketene 在 三乙胺 、 甲烷磺酰基叠氮化物 作用下， 生成 N-methyl-N-(2-propynyl)-2-diazo-3-oxobutanamide
  参考文献：
  名称：

  Rhodium(II)-catalyzed cyclization of 2-alkynyl 2-diazo-3-oxobutanoates as a method for synthesizing substituted furans

  摘要：

  A series of 2-alkynyl 2-diazo-3-oxobutanoates, when treated with a catalytic quantity of rhodium(II) acetate, were found to produce furo[3,4-c]furans in good yield. The reaction proceeds by addition of a rhodium-stabilized carbenoid onto the acetylenic pi-bond to give a vinyl carbenoid which subsequently cyclizes onto the neighboring carbonyl group to produce the furan ring. In a similar manner, indeno[1,2-c]furans were produced from 2-butynyl 2-diazoarylacetates. Compounds substituted with methyl groups on the propargylic carbon atom cyclized at a slower rate. This rate diminution is attributed to the fact that the unsubstituted propargyl group can more easily achieve the required conformation for cyclization. C-H insertion was found to compete with furan formation when an alkyl group was attached to the keto functionality of the starting diazo acetoacetate. Diazo alkynyl sulfones undergo a novel oxygen transfer reaction when treated with rhodium(II) acetate at 80-degrees-C. The cyclized product is formed by sulfone oxygen attack onto the vinyl carbenoid producing a dipolar species which subsequently collapses to give the butenolide sulfoxide.

  DOI：

  10.1021/jo00053a009

文献信息

• Stereoselective reduction of alkyl 3-oxobutanoate by carbonyl reductase from Candida magnoliae
  作者：Yoshihiko Yasohara、Noriyuki Kizaki、Junzo Hasegawa、Masaru Wada、Michihiko Kataoka、Sakayu Shimizu

  DOI：10.1016/s0957-4166(01)00279-8

  日期：2001.7

  The enantioselective reduction of alkyl 3-oxobutanoates by carbonyl reductase (Sl) from Candida magnoliae was investigated. S1 reduced alkyl 4-halo-3-oxobutanoates to the corresponding enantiomerically pure (S)-3-hydroxy esters. Escherichia coli HB101 transformant co-overproducing the S1 and glucose dehydrogenase from Bacillus megaterium, produced optically pure alkyl 4-substituted-3-hydroxybutanoates in a two-phase water/organic solvent system. (C) 2001 Elsevier Science Ltd. All rights reserved.
• TERAO, SHINJI;SHIRAISHI, MITSURU;KATO, KANEYOSHI;OHKAWA, SHIGENORI;ASHIDA+, J. CHEM. SOC. PERKIN TRANS., 1982, N 12, 2909-2920
  作者：TERAO, SHINJI、SHIRAISHI, MITSURU、KATO, KANEYOSHI、OHKAWA, SHIGENORI、ASHIDA+

  DOI：——

  日期：——
• Rhodium(II)-catalyzed cyclization of 2-alkynyl 2-diazo-3-oxobutanoates as a method for synthesizing substituted furans
  作者：Albert Padwa、Frederick R. Kinder

  DOI：10.1021/jo00053a009

  日期：1993.1

  A series of 2-alkynyl 2-diazo-3-oxobutanoates, when treated with a catalytic quantity of rhodium(II) acetate, were found to produce furo[3,4-c]furans in good yield. The reaction proceeds by addition of a rhodium-stabilized carbenoid onto the acetylenic pi-bond to give a vinyl carbenoid which subsequently cyclizes onto the neighboring carbonyl group to produce the furan ring. In a similar manner, indeno[1,2-c]furans were produced from 2-butynyl 2-diazoarylacetates. Compounds substituted with methyl groups on the propargylic carbon atom cyclized at a slower rate. This rate diminution is attributed to the fact that the unsubstituted propargyl group can more easily achieve the required conformation for cyclization. C-H insertion was found to compete with furan formation when an alkyl group was attached to the keto functionality of the starting diazo acetoacetate. Diazo alkynyl sulfones undergo a novel oxygen transfer reaction when treated with rhodium(II) acetate at 80-degrees-C. The cyclized product is formed by sulfone oxygen attack onto the vinyl carbenoid producing a dipolar species which subsequently collapses to give the butenolide sulfoxide.