(3R,4S)-4-[(S)-2,2-dimethyl-1,3-dioxolan-4-yl]-3-hydroxy-1-(p-methoxyphenyl)-3-(1-methyl-1,2-propadienyl)-2-azetidinone | 276244-14-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酰胺类
• 英文名称: (3R,4S)-4-[(S)-2,2-dimethyl-1,3-dioxolan-4-yl]-3-hydroxy-1-(p-methoxyphenyl)-3-(1-methyl-1,2-propadienyl)-2-azetidinone
• 英文别名: (+)-(3R,4S)-4-[(S)-2,2-dimethyl-1,3-dioxolan-4-yl]-3-hydroxy-3-(1-phenyl-1,2-propadienyl)-1-(p-methoxyphenyl)-2-azetidinone
• CAS: 276244-14-5
• 化学式: C₂₄H₂₅NO₅
• 分子量: 407.466
• InChiKey: QOACUTKZRCVAGM-ZFGGDYGUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  30
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  68.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (3R,4S)-4-[(S)-2,2-dimethyl-1,3-dioxolan-4-yl]-3-hydroxy-1-(p-methoxyphenyl)-3-(1-methyl-1,2-propadienyl)-2-azetidinone 在 四丁基碘化铵 、 乙酰氯 、 sodium hydroxide 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 24.0h， 以84%的产率得到(3E,4R)-4-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]-1-(4-methoxyphenyl)-3-(1-phenylprop-2-ynylidene)azetidin-2-one
  参考文献：
  名称：

  直接基于烯丙醇的立体控制进入取代的（E）-1,3-炔烃†

  摘要：

  通过用AcCl-NaOH（水溶液）处理，从芳基取代的α-烯醇中开发了一种立体选择性合成的1-取代的（E）-2-芳基-丁-1-烯-3-炔烃，包括四取代的烯烃。 。可以通过消除这种解释来解释这种转变。醋酸由δ-氢和最初形成的α-烯丙基乙酸酯中的乙酸酯基团组成。

  DOI：

  10.1039/c2ob26085a
• 作为产物：
  描述：

  (3R,4R)-4-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]-3-hydroxy-1-(4-methoxyphenyl)azetidin-2-one 在 草酰氯 、 氯化铵 、 二甲基亚砜 、 三乙胺 、 锌 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 6.0h， 生成 (3R,4S)-4-[(S)-2,2-dimethyl-1,3-dioxolan-4-yl]-3-hydroxy-1-(p-methoxyphenyl)-3-(1-methyl-1,2-propadienyl)-2-azetidinone
  参考文献：
  名称：

  Metal-Promoted Allylation, Propargylation, or Allenylation of Azetidine-2,3-diones in Aqueous and Anhydrous Media. Application to the Asymmetric Synthesis of Densely Functionalized 3-Substituted 3-Hydroxy-β-lactams

  摘要：

  Metal-mediated carbonyl allylation, allenylation, and propargylation of optically pure azetidine-2,3-diones were investigated in both anhydrous and aqueous environments. Different metals promoters showed varied regioselectivities on product formation during allenylation/propargylation reactions of the keto-beta -lactams. The stereochemistry of the new C3-substituted C3-hydroxy quaternary center was controlled by placing a chiral auxiliary at C4. In this way, the coupling of azetidine-2,3-diones with a variety of propenyl-, propynyl-, and allenylmetal reagents offers a convenient asymmetric entry to potentially bioactive 3-substituted 3-hydroxy-beta -lactams.

  DOI：

  10.1021/jo015704l

文献信息

• New Regiocontrolled Synthesis of Functionalized Pyrroles from 2-Azetidinone-Tethered Allenols
  作者：Benito Alcaide、Pedro Almendros、Rocío Carrascosa、María C. Redondo

  DOI：10.1002/chem.200700788

  日期：2008.1.7

  A new one-pot approach to synthesize densely substituted racemic and enantiopure pyrroles from beta-lactams has been developed. The approach relies on the regiocontrolled cyclization of beta-allenamine intermediates derived from the ring opening of 2-azetidinone-tethered allenols. In this approach four points of diversity are introduced, one of which is the position of the allene moiety on the beta-lactam

  已开发出一种新的一锅法，可从β-内酰胺合成密集取代的外消旋和对映纯吡咯。该方法依赖于衍生自2-氮杂环丁酮系链的烯丙醇的开环的β-亚胺胺中间体的区域控制环化。在这种方法中，引入了四个多样性点，其中之一是β-内酰胺环上丙二烯部分的位置。
• Synthesis of Spiroheterocycles by Palladium-Catalyzed Domino Cycloisomerization/Cross-Coupling of α-Allenols and Baylis-Hillman Acetates
  作者：Benito Alcaide、Pedro Almendros、Teresa Martínez del Campo、M. Teresa Quirós

  DOI：10.1002/chem.200900096

  日期：2009.3.23

  First insights into the reaction between a Baylis–Hillman adduct and an allene moiety have been obtained from the novel domino heterocyclization/cross‐coupling reaction of α‐allenols and Baylis–Hillman acetates, which furnishes [(2,5‐dihydrofuran‐3‐yl)methyl]acrylate derivatives in moderate to good yields.

  第一见解成的Baylis-希尔曼加合物和丙二烯基部分之间的反应已经从新颖多米诺heterocyclization /交叉偶联α-allenols和的Baylis-希尔曼乙酸酯的反应，其配料[（2,5-二氢呋喃-3-获得中等）的产率。
• Diversity-Oriented Preparation of Enantiopure Spirocyclic 2-Azetidinones from α-Oxo-β-lactams through Barbier-Type Reactions followed by Metal-Catalyzed Cyclizations
  作者：Benito Alcaide、Pedro Almendros、Teresa Martínez del Campo、Raquel Rodríguez-Acebes

  DOI：10.1002/adsc.200600502

  日期：2007.3.5

  Novel, simple, and convenient strategies to diversely functionalized spirocyclic β-lactams have been developed by using different metal-mediated carbonyl addition/cyclization reaction sequences. Spirocyclization precursors, 2-azetidinone-tethered homoallylic alcohols, bromohomoallylic alcohols, homopropargylic alcohols, (buta-1,3-dien-2-yl)methanols, and α-allenols have been obtained by regioselective

  通过使用不同的金属介导的羰基加成/环化反应序列，已经开发出新颖，简单和方便的策略来实现多种功能化的螺环β-内酰胺。螺环化前体，2-氮杂环丁酮拴系的均烯丙基醇，溴代均烯丙基醇，均丙炔醇，（buta-1,3-dien-2-yl）甲醇和α-烯醇是通过将稳定的有机金属试剂区域选择性地添加到氮杂环丁烷2中而获得的，3-二酮在水性环境中。上述单环不饱和醇衍生物的钌，银和钯催化的反应提供了oxaspiro-β-内酰胺。
• New Aspects of the Indium Chemistryof Carbonyl-β-lactams
  作者：Benito Alcaide、Pedro Almendros、Cristina Aragoncillo、Raquel Rodríguez-Acebes

  DOI：10.1055/s-2003-39388

  日期：——

  Reactions of racemic as well as optically pure carbonyl-β-lactams with stabilized organo-indium reagents were investigated in aqueous media. The regio- and stereochemistry of the processes were generally good, offering a convenient asymmetric entry to densely functionalized hydroxy-β-lactams.

  研究了外消旋和光学纯羰基-δ-内酰胺与稳定的有机铟试剂在水介质中的反应。反应过程的区域和立体化学性质普遍良好，为获得官能化程度较高的羟基δ-内酰胺提供了便捷的不对称途径。
• Divergent Reactivity of 2-Azetidinone-Tethered Allenols with Electrophilic Reagents: Controlled Ring Expansion<i>versus</i>Spirocyclization
  作者：Benito Alcaide、Pedro Almendros、Amparo Luna、M. Rosario Torres

  DOI：10.1002/adsc.200900864

  日期：2010.3.8

  A dual reactivity of 2‐azetidinone‐tethered allenols may occur by judicious choice of the electrophilic reagents, namely halogenating versus selenating reagents. Using common substrates, structurally different compounds, namely tetramic acids (from N‐bromosuccinimide) or spirocyclic seleno‐β‐lactams (from N‐phenylselenophthalimide), can be readily synthesized by these divergent protocols.

  明智地选择亲电试剂，即卤化试剂与硒化试剂，可能会发生2-氮杂环丁酮系链的烯丙醇的双重反应。使用常见的底物，可以通过这些不同的方案轻松合成结构上不同的化合物，即四酸（来自N-溴代琥珀酰亚胺）或螺环硒基-β-内酰胺（来自N-苯基硒代邻苯二甲酰亚胺）。