(3R,4S)-4-[(S)-2,2-dimethyl-1,3-dioxolan-4-yl]-3-hydroxy-1-benzyl-3-(1-phenyl-propa-1,2-dienyl)-azetidin-2-one | 761457-20-9

• 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-benzyl-3-(1-phenyl-propa-1,2-dienyl)-azetidin-2-one
• CAS: 761457-20-9
• 化学式: C₂₄H₂₅NO₄
• 分子量: 391.467
• InChiKey: SFTSMSVFUXECNC-ZFGGDYGUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  29
• 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：
  59
• 氢给体数：
  1
• 氢受体数：
  4

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-benzyl-3-(1-phenyl-propa-1,2-dienyl)-azetidin-2-one 在 N-溴代丁二酰亚胺(NBS) 、 三苯基膦氯金 、 水 、 silver(I) acetate 、 silver trifluoromethanesulfonate 、 四丁基碘化铵 、 对甲苯磺酸 、 乙酰氯 、 sodium hydroxide 作用下， 以 二氯甲烷 、 水 、 丙酮 为溶剂， 反应 29.5h， 生成
  参考文献：
  名称：

  Synthesis of Fused-β-Lactams through Selective Gold-Catalyzed Oxycyclization of Dioxolane-Tethered Enynes

  摘要：

  The gold-catalyzed preparation of 2-azetidinone-fused oxacycles was accomplished from beta-lactam-linked enynes through heterocyclization reaction taking advantage of the acetonide pendant group. While the synthesis of fused tetrahydrofuran-beta-lactams from 1,3-enynes could be considered as an unusual metal-catalyzed cyclization of enynols, alpha-alkoxy dioxolane-tethered 1,3-enynes exclusively undergo bis-oxycyclization to afford tricyclic bridged acetals.

  DOI：

  10.1021/jo401390k
• 作为产物：
  描述：

  (-)-(4S)-1-benzyl-4-[(S)-2,2-dimethyl-1,3-dioxolan-4-yl]-azetidine-2,3-dione 、 1-bromo-3-phenylprop-2-yne 在 indium 、 氯化铵 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 2.0h， 以98%的产率得到(3R,4S)-4-[(S)-2,2-dimethyl-1,3-dioxolan-4-yl]-3-hydroxy-1-benzyl-3-(1-phenyl-propa-1,2-dienyl)-azetidin-2-one
  参考文献：
  名称：

  通过Barbier型反应，然后通过金属催化的环化反应，从α-氧代-β-内酰胺以多样性为导向的对映纯螺环2-氮杂环丁酮类化合物的制备

  摘要：

  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。

  DOI：

  10.1002/adsc.200600502

文献信息

• Direct allenol-based stereocontrolled access to substituted (E)-1,3-enynes
  作者：Benito Alcaide、Pedro Almendros、Teresa Martínez del Campo

  DOI：10.1039/c2ob26085a

  日期：——

  A stereoselective synthesis of 1-substituted (E)-2-aryl-but-1-en-3-ynes, including tetrasubstituted alkenes, has been developed from aryl-substituted α-allenols by treatment with the AcCl–NaOH (aqueous) system. This transformation might be explained through the elimination of acetic acid, made up of a δ-hydrogen and the acetate group in the initially formed α-allenic acetate.

  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。
• Pd-Cu Bimetallic Catalyzed Domino Cyclization of α-Allenols Followed by a Coupling Reaction: New Sequence Leading to Functionalized Spirolactams
  作者：Benito Alcaide、Pedro Almendros、Raquel Rodríguez-Acebes

  DOI：10.1002/chem.200500228

  日期：2005.9.19

  A novel regioselective metal-catalyzed spirocyclization of alpha-allenols-cross coupling (Heck, Sonogashira, and Suzuki) reaction sequence, leading to potentially bioactive spirocyclic lactam derivatives has been developed. Precursors for the tandem spirocyclization-coupling reaction, alpha-allenols 2 a-d were obtained starting from alpha-oxolactams 1 a-c via indium-mediated Barbier-type carbonyl-allenylation

  已经开发出新颖的区域选择性金属催化的α-烯醇-交叉偶联（Heck，Sonogashira和Suzuki）反应序列的螺环化，从而导致潜在的生物活性螺环内酰胺衍生物。使用我们之前描述的方法，在水性介质中，通过铟介导的Barbier型羰基-烯基化反应，从α-氧代内酰胺1 ac开始，进行串联螺环化偶联反应的前体α-allenols2 ad。
• 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）。
• Controlled Rearrangement of Lactam-Tethered Allenols with Brominating Reagents: A Combined Experimental and Theoretical Study on α- versus β-Keto Lactam Formation
  作者：Benito Alcaide、Pedro Almendros、Amparo Luna、Sara Cembellín、Manuel Arnó、Luis R. Domingo

  DOI：10.1002/chem.201101160

  日期：2011.10.4

  expansion of lactam‐tethered allenols to efficiently afford cyclic α‐ or β‐ketoamides with good yields and high chemo‐, regio‐, and diastereoselectivity, through controlled CC bond cleavage of the β‐ or γ‐lactam nucleus. Interestingly, in contrast to the rearrangement reactions of 2‐azetidinone‐tethered allenols, which lead to the corresponding tetramic acid derivatives (β‐keto lactam adducts) as the

  Ñ溴代琥珀酰亚胺（NBS）顺利促进内酰胺拴allenols的环扩展以有效地得到环状α-或β酮酰胺具有良好的产率和高的化学-选择性，区域选择性和非对映选择性，通过控制Ç 的β的C键裂解γ或γ-内酰胺核。有趣的是，与2-氮杂环丁酮-系留的烯丙醇的重排反应形成唯一的产物相应的四酸衍生物（β-酮内酰胺加合物）相反，在相似条件下2-吲哚酮-系留的烯丙醇的反应产生了喹啉。 -2,3-二酮（α-酮内酰胺加成物）作为独家产品或主要产品。为了使实验观察合理化，已经进行了理论研究。
• An Alternative to Precious Metals: Hg(ClO₄)₂·3H₂O as a Cheap and Water-Tolerant Catalyst for the Cycloisomerization of Allenols
  作者：Benito Alcaide、Pedro Almendros、Amparo Luna、Elena Soriano

  DOI：10.1021/acs.joc.5b00887

  日期：2015.7.17

  Hg(ClO4)(2)center dot 3H(2)O, a cheap, water-tolerant, and stable salt, catalyzes the cydoisomerization reaction or alpha-allenols to 2,5-dihydrofurans in an efficient and selective manner. The reaction is general and can be applied to differently functionalized substrates, including alkyl-substituted, aryl-substituted, enantiopure, and tertiary allenols. In addition, density functional theory (DFT) calculations were performed to obtain insight into various aspects of the controlled reactivity of a-allenols under mercury catalysis. They suggest a dual activation of the allenol by the Hg complex that drives the reaction to the chemoselective formation of 2,5-dihydrofurans.