(S)-tert-butyl 2-chloro-1-oxo-2,3-dihydro-1H-indene-2-carboxylate | 1280485-80-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚满类
• 英文名称: (S)-tert-butyl 2-chloro-1-oxo-2,3-dihydro-1H-indene-2-carboxylate
• 英文别名: tert-butyl (S)-2-chloro-1-oxo-2,3-dihydro-1H-indene-2-carboxylate；tert-butyl (S)-2-chloro-2,3-dihydro-1-oxo-1H-indene-2-carboxylate；tert-butyl 2-chloro-1-oxo-2,3-dihydro-1H-indene-2-carboxylate；t-butyl 2-chloro-2,3-dihydro-1-oxo-1H-indene-2-carboxylate；tert-butyl (2S)-2-chloro-3-oxo-1H-indene-2-carboxylate
• CAS: 1280485-80-4
• 化学式: C₁₄H₁₅ClO₃
• 分子量: 266.724
• InChiKey: SSSLJYCVPWPPGL-AWEZNQCLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.43
• 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：

  (S)-tert-butyl 2-chloro-1-oxo-2,3-dihydro-1H-indene-2-carboxylate 在 sodium azide 、 20% Pd-BaSO4 作用下， 以 甲醇 、 二甲基亚砜 为溶剂， 反应 20.0h， 生成 t-butyl 2-amino-2,3-dihydro-1-hydroxy-1H-indene-2-carboxylate
  参考文献：
  名称：

  Highly Enantioselective Chlorination of β-Keto Esters and Subsequent S_N2 Displacement of Tertiary Chlorides: A Flexible Method for the Construction of Quaternary Stereogenic Centers

  摘要：

  Highly enantioselective chlorination of beta-oxo esters and subsequent stereospecific substitution of tertiary chlorides are described. Enantioselective chlorination of beta-keto esters and malonates was performed using a chiral Lewis acid catalyst prepared from Cu(OTf)(2) and the newly developed spirooxazoline ligand 2 to yield the desired a-chlorinated products with high enantioselectivity (up to 98% ee). Nucleophilic substitution of the resulting chlorides proceeded smoothly to afford a variety of chiral molecules such as alpha-amino, alpha-allcylthio, and alpha-fluoro esters, without loss of enantiopurity. The results of X-ray crystallographic analysis proved that Walden inversion occurs at the chlorinated tertiary carbon center. These results supported the fact that the substitution proceeds via an S(N)2 mechanism.

  DOI：

  10.1021/ja304806j
• 作为产物：
  描述：

  tert-butyl 2,3-dihydro-1-oxo-1H-indene-2-carboxylate 在 N-氯代丁二酰亚胺 、 C₃₄H₂₄N₂O 、 copper(II) bis(trifluoromethanesulfonate) 作用下， 以 甲苯 为溶剂， 反应 1.0h， 以95%的产率得到(S)-tert-butyl 2-chloro-1-oxo-2,3-dihydro-1H-indene-2-carboxylate
  参考文献：
  名称：

  在叔立体碳上用酚类合成威廉姆森醚：β-酮基酯的形式对映选择性苯氧基化

  摘要：

  首次描述了α-芳氧基-β-酮酸酯的对映选择性形成。路易斯酸催化β-酮酯的对映选择性氯化，随后与酚进行S N 2反应，生成ee高达96％的α-芳氧基-β-酮酯 。还发现α-氯-β-酮基酯的Favorskii重排产生1,2-二酯，其对映体纯度略有降低。

  DOI：

  10.1002/chem.201502042

文献信息

• Asymmetric Chlorination of β-Keto Esters Using Diaminomethylenemalononitrile Organocatalyst
  作者：Takaaki Sakai、Shin-ichi Hirashima、Kosuke Nakashima、Chie Maeda、Akihiro Yoshida、Yuji Koseki、Tsuyoshi Miura

  DOI：10.1248/cpb.c16-00722

  日期：——

  Diaminomethylenemalononitrile organocatalysts promote the asymmetric chlorination of simple cyclic beta-keto esters such as methyl, ethyl, and benzyl esters of 1-oxo-2,3-dihydro-1H-indene-2-carboxylic acid. This affords the corresponding chiral alpha-chlorinated carbonyl products in excellent yields with high enantioselectivities.

  二氨基亚甲基丙二腈有机催化剂促进简单的环状β-酮酯（例如1-氧代-2，3-二氢-1H-茚-2-羧酸的甲基，乙基和苄基酯）的不对称氯化。这以高收率和高对映选择性提供了相应的手性α-氯化羰基产物。
• Enantioselective α-chlorination of β-keto esters and amides catalyzed by chiral imidodiphosphoric acids
  作者：Xukai Guan、Dong An、Guofeng Liu、Heng Zhang、Jigang Gao、Tianyun Zhou、Guangliang Zhang、Suoqin Zhang

  DOI：10.1016/j.tetlet.2018.05.024

  日期：2018.6

  Chiral imidodiphosphoric acids were employed as catalysts for the enantioselective α-chlorination of β-keto esters and amides using NCS as the chlorine source, providing a series of optically active products with good to high enantioselectivities (74–95% ee) and excellent yields (92–99%). This represents the first report of the Brønsted acid catalyzed enantioselective α-chlorination of cyclic β-keto

  手性酸imidodiphosphoric被雇用作为催化剂用于对映选择性α的-chlorination β酮酯和使用NCS作为氯源，提供一系列的光学活性产物具有良好的高对映选择性（74-95％ee）和优良产率的酰胺（ 92–99％）。这代表了布朗斯台德酸催化的环状β-酮衍生物对映选择性α-氯化反应的首次报道。
• Asymmetric α‐Chlorination of β‐Keto Esters Using Hypervalent Iodine‐Based Cl‐Transfer Reagents in Combination with Cinchona Alkaloid Catalysts
  作者：Lotte Stockhammer、Johannes Schörgenhumer、Christopher Mairhofer、Mario Waser

  DOI：10.1002/ejoc.202001217

  日期：2021.1.8

  Simple Cinchona alkaloids serve as nucleophilic organocatalysts to facilitate the enantioselective α‐chlorination of β‐keto esters by using hypervalent iodine‐based Cl‐transfer reagents

  简单的金鸡纳生物碱作为亲核有机催化剂，通过使用高价碘基 Cl 转移试剂促进 β-酮酯的对映选择性 α-氯化
• Asymmetric Chlorination of Cyclic β-Keto Esters and N-Boc Oxindoles­ Catalyzed by an Iron(III)-BPsalan Complex
  作者：Zhen-Jiang Xu、Chi-Ming Che、Yong-Heng Luo、Yuan-Ji Ping、Zong-Rui Li、Xin Gu

  DOI：10.1055/s-0036-1590955

  日期：2018.3

  Abstract An iron(III)-BPsalan complex was found to efficiently catalyze the asymmetric chlorination reaction of cyclic β-keto esters and N-Boc oxindoles, affording the corresponding chlorinated products in high yield and up to 92% ee with NCS as chlorination reagent under mild reaction conditions. An iron(III)-BPsalan complex was found to efficiently catalyze the asymmetric chlorination reaction of

  摘要 发现铁（III）-BPsalan络合物可有效催化环状β-酮酯和N - Boc羟吲哚的不对称氯化反应，在温和的条件下以NCS作为氯化试剂，可提供高产率和高达92％ee的相应氯化产物。反应条件。 发现铁（III）-BPsalan络合物可有效催化环状β-酮酯和N - Boc羟吲哚的不对称氯化反应，在温和的条件下以NCS作为氯化试剂，可提供高产率和高达92％ee的相应氯化产物。反应条件。
• Catalytic enantioselective chlorination of cyclic β-keto esters in the presence of chiral Pd(II) complexes
  作者：Young Ku Kang、Hee Hun Kim、Kwang Oh Koh、Dae Young Kim

  DOI：10.1016/j.tetlet.2012.05.064

  日期：2012.7

  The catalytic enantioselective electrophilic chlorination promoted by chiral palladium complexes is described. The treatment of β-keto esters with 2,3,4,5,6,6-hexachlorocyclohex-2,4-dienone as chlorine source under mild reaction conditions afforded the corresponding α-chlorinated β-keto esters with excellent enantioselectivities (up to 94% ee).

  描述了由手性钯配合物促进的催化对映选择性亲电子氯化。在温和的反应条件下，用2,3,4,5,6,6-六氯环己基-2,4-二烯酮作为氯源处理β-酮酯，得到相应的α-氯代β-酮酯，其对映选择性极好（最高可达94％ee）。