methyl 3-((tert-butoxycarbonyl)oxy)-2-methylenepentanoate | 1316312-91-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: methyl 3-((tert-butoxycarbonyl)oxy)-2-methylenepentanoate
• CAS: 1316312-91-0
• 化学式: C₁₂H₂₀O₅
• 分子量: 244.288
• InChiKey: DZWWGLQTZOSMHV-UHFFFAOYSA-N

物化性质

• 沸点：
  287.8±33.0 °C(Predicted)
• 密度：
  1.038±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.45
• 重原子数：
  17.0
• 可旋转键数：
  4.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  61.83
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  methyl 3-((tert-butoxycarbonyl)oxy)-2-methylenepentanoate 在 三乙烯二胺 、 水 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 12.0h， 以60%的产率得到3-hydroxy-2-methylene-pentanoic acid methyl ester
  参考文献：
  名称：

  Lewis Base Catalyzed Enantioselective Allylic Hydroxylation of Morita–Baylis–Hillman Carbonates with Water

  摘要：

  A Lewis base catalyzed allylic hydroxylation of Morita-Baylis-Hillman (MBH) carbonates has been developed. Various chiral MBH alcohols can be synthesized in high yields (up to 99%) and excellent enantioselectivities (up to 94% ee). This is the first report using water as a nucleophile in asymmetric organocatalysis. The nucleophilic role of water has been verified using O-18-labeling experiments.

  DOI：

  10.1021/jo201096e

文献信息

• A Facile Cu(I)/BINAP-Catalyzed Asymmetric Approach to Functionalized Pyroglutamate Derivatives Bearing a Unique Quaternary Stereogenic Center
  作者：Huai-Long Teng、Fei-Long Luo、Hai-Yan Tao、Chun-Jiang Wang

  DOI：10.1021/ol202326j

  日期：2011.10.21

  pyroglutamate derivatives bearing a unique quaternary stereogenic center has been developed via Cu(I)/BINAP-catalyzed tandem Michael addition–elimination of α-substituted aldimino esters with Morita–Baylis–Hillman (MBH) carbonates followed by a deprotection/lactamization protocol, which performs well over a broad scope of substrates and provides biologically active pyroglutamate derivatives in good yields

  通过Cu（I）/ BINAP催化的串联Michael加成反应，可以直接，轻松地获得带有独特的季生立体中心的对映体富集的焦谷氨酸衍生物，然后用Morita-Baylis-Hillman（MBH）碳酸盐消除α-取代的醛糖基酯一种脱保护/内酰胺化方案，该方案在广泛的底物上表现良好，并以良好的收率和优异的对映选择性提供了具有生物活性的焦谷氨酸衍生物。
• A Highly Regio- and Diastereoselective Phosphane-Catalyzed [3+2] Annulation of Morita-Baylis-Hillman Carbonates with Cyclic<i>N</i>-Acyl Ketimines
  作者：Li-Jun Yang、Hua Cai、Jing Nie、Jun-An Ma

  DOI：10.1002/ejoc.201300342

  日期：2013.7

  A highly regio- and diastereoselective phosphane-catalyzed [3+2] annulation of Morita–Baylis–Hillman (MBH) carbonates with cyclic N-acyl-substituted ketimines was developed. In the presence of the catalyst PBu3 (10 mol-%), a series of N-fused tricyclic products were obtained in excellent yields and diastereoselectivities under mild conditions. An example of a catalytic enantioselective annulation is

  开发了一种高度区域选择性和非对映选择性磷烷催化的 Morita-Baylis-Hillman (MBH) 碳酸酯与环状 N-酰基取代的酮亚胺的 [3+2] 环化。在催化剂 PBu3 (10 mol-%) 存在下，在温和条件下以优异的产率和非对映选择性获得了一系列 N-稠合三环产物。还介绍了催化对映选择性环化的一个例子。
• Chiral Phosphine-Catalyzed Enantioselective [3+2] Annulation of Morita-Baylis-Hillman Carbonates with Cyclic 1-Azadienes: Synthesis of Functionalized Cyclopentenes
  作者：Yang Wu、Yang Liu、Wenjun Yang、Honglei Liu、Leijie Zhou、Zhanhu Sun、Hongchao Guo

  DOI：10.1002/adsc.201600607

  日期：2016.11.17

  catalyst, the asymmetric [3+2] annulation of Morita–Baylis–Hillman carbonates with cyclic 1‐azadienes proceeded smoothly under mild conditions to give various enantiomerically enriched cyclopentene derivatives bearing three consecutive tertiary stereocenters and a sulfamate moiety in moderate to excellent yields with moderate to excellent enantioselectivities and excellent diastereoselectivities.

  使用双官能手性膦作为催化剂，森田-贝利斯-希尔曼碳酸盐与环状1-氮杂二烯的不对称[3 + 2]环化在温和条件下顺利进行，得到了具有三个连续的三级立体中心的各种对映体富集的环戊烯衍生物。氨基磺酸盐部分，具有中等至优异的收率，具有中等至优异的对映选择性和出色的非对映选择性。
• Copper/Lewis base cooperatively catalyzed asymmetric allylic alkylation of Morita–Baylis–Hillman carbonates with azomethine ylides
  作者：Yimin Hu、Zhengyang Yan、Wangyu Shi、Jianning Liao、Min Liu、Ting Pan、Wei Wang、Yongjun Wu、Xianghong Hao、Hongchao Guo

  DOI：10.1039/d1cc02861h

  日期：——

  In this paper, an asymmetric allylic alkylation of easily available azomethine ylides with Morita–Baylis–Hillman (MBH) carbonates through a copper (I)/Lewis base cooperative catalysis strategy has been realized. The co-catalyzed asymmetric allylic alkylation provided the corresponding amino acid derivatives in up to 90% yields with up to 99% ee as well as good to excellent regioselectivity.

  在本文中，通过铜（I）/刘易斯碱协同催化策略实现了易于获得的偶氮甲碱叶立德与 Morita-Baylis-Hillman（MBH）碳酸酯的不对称烯丙基烷基化。共催化的不对称烯丙基烷基化以高达 90% 的产率和高达 99% 的 ee 以及良好至极好的区域选择性提供了相应的氨基酸衍生物。
• Facile synthesis of novel tetrasubstituted 1-pyrazolines from Baylis–Hillman adducts and acyl diazomethanes
  作者：Hongbao Sun、Xiaoyan Wang、Miao Zhan、Jie Liu、Yongmei Xie

  DOI：10.1016/j.tetlet.2013.05.041

  日期：2013.7

  An efficient method for the regioselective synthesis of potentially biologically active tetrasubstituted 1-pyrazolines has been achieved via a 1,3-dipolar cycloaddition reaction. A range of tetrasubstituted 1-pyrazolines bearing one Boc group and two ester groups were obtained in high yields (up to 99%). The structure and relative stereochemistry of cycloadducts were confirmed by NMR spectra and single

  已经通过1，3-偶极环加成反应实现了潜在的具有生物活性的四取代的1-吡唑啉的区域选择性合成的有效方法。以高收率（高达99％）获得了一系列带有一个Boc基团和两个酯基的四取代1-吡唑啉。通过NMR光谱和单晶X射线衍射证实了环加合物的结构和相对立体化学。提出了可能的机理，并且可以通过色谱法将作为单一非对映异构体的主要Z-环加合物彼此分离。