(3RS,4SR)-3-benzoyl-4-methyloxetan-2-one

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3RS,4SR)-3-benzoyl-4-methyloxetan-2-one
• 英文别名: trans-3-benzoyl-4-methyloxetan-2-one；3-benzoyl-4-methyloxetan-2-one；(3R,4S)-3-benzoyl-4-methyloxetan-2-one
• 化学式: C₁₁H₁₀O₃
• 分子量: 190.199
• InChiKey: WSDSWTJPOALLCU-IONNQARKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  苯甲酸烯丙酯 、 (3RS,4SR)-3-benzoyl-4-methyloxetan-2-one 在 bis(η3-allyl-μ-chloropalladium(II)) 、 4,5-双二苯基膦-9,9-二甲基氧杂蒽 作用下， 以 甲苯 为溶剂， 反应 4.0h， 以85%的产率得到3-allyl-3-benzoyl-4-methyloxetan-2-one
  参考文献：
  名称：

  中继Rh（II）/ Pd（0）双重催化：循环全四元碳中心的选择性构建

  摘要：

  开发了一种新型的中继Rh（II）/ Pd（0）双重催化策略，该策略可促进α-重氮羰基化合物与烯丙基羧酸盐的发散反应，从而选择性地构建环状全季碳中心。这种二元催化剂体系在温和的条件下使多米诺骨牌CH插入/烯丙基烷基化过程成为可能。值得注意的是，多米诺骨牌催化反应显示出良好的选择性和对各种功能的优异耐受性，并且操作简单。

  DOI：

  10.1021/acs.orglett.6b02958
• 作为产物：
  描述：

  (1Z)-2-偶氮基-1-乙氧基-3-氧代-3-苯基-1-丙烯-1-醇 在 rhodium(II) pivalate 作用下， 以 甲苯 为溶剂， 反应 1.0h， 以61%的产率得到(3RS,4SR)-3-benzoyl-4-methyloxetan-2-one
  参考文献：
  名称：

  中继Rh（II）/ Pd（0）双重催化：循环全四元碳中心的选择性构建

  摘要：

  开发了一种新型的中继Rh（II）/ Pd（0）双重催化策略，该策略可促进α-重氮羰基化合物与烯丙基羧酸盐的发散反应，从而选择性地构建环状全季碳中心。这种二元催化剂体系在温和的条件下使多米诺骨牌CH插入/烯丙基烷基化过程成为可能。值得注意的是，多米诺骨牌催化反应显示出良好的选择性和对各种功能的优异耐受性，并且操作简单。

  DOI：

  10.1021/acs.orglett.6b02958

文献信息

• Displacement of Dinitrogen by Oxygen: A Methodology for the Catalytic Conversion of Diazocarbonyl Compounds to Ketocarbonyl Compounds by 2,6-Dichloropyridine-<i>N</i>-oxide
  作者：Yang Yu、Qiang Sha、Hui Cui、Kory S. Chandler、Michael P. Doyle

  DOI：10.1021/acs.orglett.7b03912

  日期：2018.2.2

  Dirhodium(II) catalyzed dinitrogen extrusion from diazocarbonyl compounds by 2,6-dichloropyridine-N-oxide forms ketocarbonyl compounds in near-quantitative yields. Reactions occur at room temperature, and the pyridine product does not coordinate with dirhodium(II) to inhibit catalysis. Anhydrous tricarbonyl compounds, as well as dicarbonyl compounds, are conveniently prepared by this methodology, and

  重氮（II）催化的重氮通过2,6-二氯吡啶-N-氧化物从重氮羰基化合物中挤出，以接近定量的产率形成酮羰基化合物。反应在室温下发生，并且吡啶产物不与二氢吡啶鎓（II）配位以抑制催化作用。通过这种方法可以方便地制备无水三羰基化合物以及二羰基化合物，并且它们已就地用于催化烯和羟醛的转化。
• Synthesis of electron-poor 4-halo-2-azabuta-1,3-dienes by Rh(II)-catalyzed diazo ester–azirine coupling. 2-Azabuta-1,3-diene-2,3-dihydroazete valence isomerism
  作者：Mikhail S. Novikov、Ilia A. Smetanin、Alexander F. Khlebnikov、Nikolai V. Rostovskii、Dmitry S. Yufit

  DOI：10.1016/j.tetlet.2012.08.063

  日期：2012.10

  dimethyl diazomalonate with methyl 2-bromo- and 2-chloro-3-phenyl-2H-azirine-2-carboxylates gives rise to electron-poor 4-halo-substituted (3E)-2-azabuta-1,3-dienes. Their formation proceeds with complete stereoselectivity via ring-opening of the intermediate azirinium ylide. 2-Azabuta-1,3-dienes with electron-withdrawing substituents at the 1,1,4-positions are stable compounds at room temperature, but

  Rh 2（OAc）4催化2-酰基-2-重氮乙酸烷基酯和重氮丙二酸二甲酯与2-溴-和2-氯-3-苯基-2 H-叠氮基-2-羧酸甲酯的反应弱的4-卤代（3 E）-2-azabuta-1,3-二烯。它们的形成通过中间的叠氮基内鎓盐的开环以完全的立体选择性进行。在1,1,4-位置带有吸电子取代基的2-氮杂丁1,3-二烯在室温下是稳定的化合物，但在高温下与环状价异构体2,3-二氢氮杂环丁烷处于平衡状态。
• Serine and Threonine β-Lactones:  A New Class of Hepatitis A Virus 3C Cysteine Proteinase Inhibitors
  作者：Manjinder S. Lall、Yeeman K. Ramtohul、Michael N. G. James、John C. Vederas

  DOI：10.1021/jo0109016

  日期：2002.3.1

  Hepatitis A virus (HAV) 3C enzyme is a cysteine proteinase essential for viral replication and infectivity and represents a target for the development of antiviral drugs. A number of serine and threonine beta-lactones were synthesized and tested against HAV 3C proteinase. The D-N-Cbz-serine beta-lactone 5a displays competitive reversible inhibition with a K-i value of 1.50 x 10(-6) M. Its enantiomer, L-N-Cbz-serine beta-lactone 5b is an irreversible inactivator with 0.70 min(-1), K, = 1.84 x 10(-4) M and k(inact)/K-I = 3800 M-1 min(-1). Mass spectrometry and HMQC NMR studies using C-13-labeled 5b show that inactivation of the enzyme occurs by nucleophilic attack of the cysteine thiol (Cys-172) at the beta-position of the oxetanone ring. Although the N-Cbz-serine beta-lactones 5a and 5b display potent inhibition, other related analogues with an N-Cbz side chain, such as the five-membered ring homoserine gamma-lactones 14a and 14b, the four-membered ring beta-lactam 33, 2-methylene oxetane 34, cyclobutanone 36, and 3-azetidinone 39, fail to give significant inhibition of HAV 3C proteinase, thus demonstrating the importance of the beta-lactone ring for binding.
• 4-Halo-2-azabuta-1,3-dienes as intermediates in the rhodium carbenoid-initiated transformation of 2-halo-2H-azirines into 2,3-dihydroazetes and 2,5-dihydrooxazoles
  作者：Ilia A. Smetanin、Mikhail S. Novikov、Nikolai V. Rostovskii、Alexander F. Khlebnikov、Galina L. Starova、Dmitry S. Yufit

  DOI：10.1016/j.tet.2015.05.022

  日期：2015.7

  A wide range of electron-poor 4-bromo-/4-chloro-2-azabuta-1,3-dienes were synthesized by the Rh-2(OAc)(4)-catalyzed reaction of diazo esters and diazo ketones with methyl 2-halo-2H-azirine-2-carboxylates. The E stereoselectivity with respect to the configuration of the C=C bond of the 2-azadiene moiety is in good agreement with the results of DFT (M06-2X/6-31+G(d,p)) calculations of the reaction pathway. The reaction proceeds via the formation of an azirinium ylide intermediate followed by ring opening with outward rotation of the halogen atom. Depending on the substitution pattern at C-1 electron-poor 4-halo-2-azabutadienes can undergo two types of cyclization at elevated temperatures: reversible 1,4-electrocyclization to give 2,3-dihydroazetes or 1,5-exo-trig cyclization to give 5-methylene-2,5-dihydrooxazoles, both in good yields. The dihydrooxazole derivatives can be also obtained at ambient temperature under DBU catalysis. (C) 2015 Elsevier Ltd. All rights reserved.
• Site selective CH insertion of unactivated α-diazo-α-aroyl esters catalysed by Rh(II) carboxylates
  作者：B.S. Balaji、Bhanu M. Chanda

  DOI：10.1016/s0040-4039(98)01314-8

  日期：1998.8

  The results from the study of C-H insertion of unactivated alpha-diazo-alpha-aroyl esters catalysed by rhodium(II) carboxylates which give beta-lactones indicate that steric effects may play a major role in product formation. (C) 1998 Published by Elsevier Science Ltd. All rights reserved.