tert-butyl (S)-2-chloro-1,2,3,4-tetrahydro-1-oxonaphthalene-2-carboxylate | 1381800-64-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: tert-butyl (S)-2-chloro-1,2,3,4-tetrahydro-1-oxonaphthalene-2-carboxylate
• 英文别名: tert-butyl 2-chloro-1-oxo-1,2,3,4-tetrahydronaphthalene-2-carboxylate；t-butyl 2-chloro-1,2,3,4-tetrahydro-1-oxonaphthalene-2-carboxylate；tert-butyl (2S)-2-chloro-1-oxo-3,4-dihydronaphthalene-2-carboxylate
• CAS: 1381800-64-1
• 化学式: C₁₅H₁₇ClO₃
• 分子量: 280.751
• InChiKey: LNPPEPGUUSKCKU-HNNXBMFYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 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：

  tert-butyl (S)-2-chloro-1,2,3,4-tetrahydro-1-oxonaphthalene-2-carboxylate 在 sodium azide 、 20% Pd-BaSO4 作用下， 以 甲醇 、 二甲基亚砜 为溶剂， 反应 6.0h， 生成 t-butyl 2-amino-1,2,3,4-tetrahydro-1-hydroxynaphthalene-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：

  1-吡咯甲酸叔丁酯 在 N-氯代丁二酰亚胺 、 C₃₅H₂₆N₂O₂ 、 copper(II) bis(trifluoromethanesulfonate) 、 sodium hydride 作用下， 以 苯 为溶剂， 生成 tert-butyl (S)-2-chloro-1,2,3,4-tetrahydro-1-oxonaphthalene-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

文献信息

• Williamson Ether Synthesis with Phenols at a Tertiary Stereogenic Carbon: Formal Enantioselective Phenoxylation of β‐Keto Esters
  作者：Kazutaka Shibatomi、Manato Kotozaki、Nozomi Sasaki、Ikuhide Fujisawa、Seiji Iwasa

  DOI：10.1002/chem.201502042

  日期：2015.9.28

  The enantioselective formation of α‐aryloxy‐β‐keto esters is described for the first time. Lewis acid catalyzed enantioselective chlorination of β‐keto esters and subsequent SN2 reactions with phenols yielded α‐aryloxy‐β‐keto esters with up to 96 % ee. Favorskii rearrangement of α‐chloro‐β‐keto esters was also found to give 1,2‐diesters with slightly reduced enantiopurity.

  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。
• Stereoselective α-Chlorination of β-Keto Esters in the Presence of Hybrid Amide-Based <i>Cinchona</i> Alkaloids as Catalysts
  作者：Maciej Majdecki、Piotr Grodek、Janusz Jurczak

  DOI：10.1021/acs.joc.0c02486

  日期：2021.1.1

  by hybrid amide-based Cinchona derivatives. The chlorination process proceeds with proper quantitative yields (up to <99%) and high asymmetric induction (up to 97% ee). We show that the use of only 0.5 mol % hybrid catalyst based on a Cinchona core allows the chlorination reaction to be conducted in a highly enantioselective manner with various indanone and tetralone carboxylate esters.

  我们报道了基于杂化酰胺基金鸡纳衍生物催化的β-酮酯的对映选择性相转移α-氯化。氯化过程以适当的定量收率（最高<99％）和高度不对称诱导（最高97％ee）进行。我们显示基于金鸡纳核仅使用0.5摩尔％的杂化催化剂允许使用多种茚满酮和四氢萘酮羧酸酯以高度对映选择性的方式进行氯化反应。
• 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。
• 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
  作者：Kazutaka Shibatomi、Yoshinori Soga、Akira Narayama、Ikuhide Fujisawa、Seiji Iwasa

  DOI：10.1021/ja304806j

  日期：2012.6.20

  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.