(R)-(-)-1',2'-dihydro-1'-methyl-2'-oxospiro[1,4-dioxaspiro[4.5]dec-6-ene-8,3'-3'H-indole] | 142613-63-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: (R)-(-)-1',2'-dihydro-1'-methyl-2'-oxospiro[1,4-dioxaspiro[4.5]dec-6-ene-8,3'-3'H-indole]
• CAS: 142613-63-6
• 化学式: C₁₆H₁₇NO₃
• 分子量: 271.316
• InChiKey: UHYPBRJQOHSTQE-HNNXBMFYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  20
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  38.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  2-hydroxy-(1,4-dioxaspiro[4.5]dec-7-en-8-ylcarbonyl)-N-methylaniline 在 tris(dibenzylideneacetone)dipalladium (0) 吡啶 、 4-二甲氨基吡啶 、 chiral phosphino-bis(3,5-difluorophenyl)imidazoline 、 pentamethylpiperidine 作用下， 以 二苯醚 、 二氯甲烷 为溶剂， 反应 20.0h， 生成 (R)-(-)-1',2'-dihydro-1'-methyl-2'-oxospiro[1,4-dioxaspiro[4.5]dec-6-ene-8,3'-3'H-indole]
  参考文献：
  名称：

  Electronic Control of Chiral Quaternary Center Creation in the Intramolecular Asymmetric Heck Reaction

  摘要：

  The Boehringer-Ingelheim phosphinoimidazoline (BIPI) ligands were applied to the formation of chiral quaternary centers in the asymmetric Heck reaction. Several different substrates were examined in detail, using more than 70 members of this new ligand class. Hammett relationships were determined through systematic variation of the ligand electronics. All substrates showed essentially the same Hammett behavior, where enantioselectivity increased as the ligands were made more electron-deficient. Ligand optimization has led to catalysts which give the highest enantioselectivities reported to date for these difficult systems.

  DOI：

  10.1021/jo049448z

文献信息

• Catalytic Asymmetric Synthesis of Quaternary Carbon Centers. Exploratory Investigations of Intramolecular Heck Reactions of (<i>E</i>)-α,β-Unsaturated 2-Haloanilides and Analogues To Form Enantioenriched Spirocyclic Products
  作者：Atsuyuki Ashimori、Benoit Bachand、Larry E. Overman、Daniel J. Poon

  DOI：10.1021/ja980786p

  日期：1998.7.1

  Using Pd−BINAP as catalyst, a variety of enantioenriched 3,3-disubstituted oxindoles, indolines, and dihydrobenzofurans was prepared from (E)-α,β-unsaturated 2-haloaniline substrates (Table 5). With but one exception, cyclizations conducted in the presence of Ag3PO4 or 1,2,2,6,6-pentamethylpiperidine (PMP) afforded opposite enantiomers of the spirocyclic product. Which HI acceptor results in highest enantioselection

  研究了手性二膦结构、催化剂生成方法、反应溶剂和 HI 清除剂对从 4 的不对称 Heck 环化形成富含对映体的 3,3-二取代 2-羟吲哚 5 的影响（方程式 1）。取决于 HI 清除剂是银盐还是碱性叔胺，使用 BINAP 的相同对映异构体可以以良好的选择性形成 5 的任一对映异构体。使用 Pd-BINAP 作为催化剂，从 (E)-α,β-不饱和 2-卤代苯胺底物制备了多种对映体富集的 3,3-二取代羟吲哚、二氢吲哚和二氢苯并呋喃（表 5）。除了一个例外，在 Ag3PO4 或 1,2,2,6,6-五甲基哌啶 (PMP) 存在下进行的环化提供了螺环产物的相反对映异构体。哪个 HI 受体导致最高的对映选择取决于底物。
• Catalytic asymmetric synthesis of quarternary carbon centers. Palladium-catalyzed formation of either enantiomer of spirooxindoles and related spirocyclics using a single enantiomer of a chiral diphosphine ligand
  作者：Atsuyuki Ashimori、Larry E. Overman

  DOI：10.1021/jo00043a005

  日期：1992.8

  The asymmetric synthesis of eight spirooxindoles and related spirocyclics from the corresponding aryl iodide by palladium catalyzed cyclizations in the presence of the diphosphine ligand (R)-(+)-BINAP is reported.