S_s-2-methyl-propane-2-sulfinic acid [3-methyl-butylidene]amide | 948843-33-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 亚磺酸及其衍生物
• 英文名称: S_s-2-methyl-propane-2-sulfinic acid [3-methyl-butylidene]amide
• 英文别名: (S)-2-methyl-N-(3-methylbutylidene)propane-2-sulfinamide；(S,E)-2-methyl-N-(3-methylbutylidene)propane-2-sulfinamide
• CAS: 948843-33-2
• 化学式: C₉H₁₉NOS
• 分子量: 189.322
• InChiKey: SURNLDMUXHLWDG-LBPRGKRZSA-N

物化性质

• 沸点：
  279.2±23.0 °C(Predicted)
• 密度：
  0.98±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  48.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  S_s-2-methyl-propane-2-sulfinic acid [3-methyl-butylidene]amide 在 rubidium carbonate 、 盐酸 、 溴 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 15.0h， 生成 (R)-benzyl N-[1-(dimethoxyphosphoryl)-3-methylbutyl]carbamate
  参考文献：
  名称：

  Enantioselective Synthesis of H-Phosphinic Acids Bearing Natural Amino Acid Residues

  摘要：

  The first systematic study on the asymmetric synthesis of H-phosphinic acids bearing natural protein amino acid residues was reported on the basis of the asymmetric addition of ethyl diethoxymethylphosphinate to N-tert-butane-sulfinyl imines. Good yields and moderate to high enantiose-lectivities were obtained. Reliable methods were developed for the elucidation of the stereochemistry of these phosphinic acids and derivatives thereof. The transformation of the side chains of these analogues was studied. Methods for the conversion of the alpha-aminophosphinates to oligopetides were reported.

  DOI：

  10.1021/jo400798f
• 作为产物：
  描述：

  异戊醛 、 S-叔丁基亚磺酰胺 在 titanium(IV) tetraethanolate 作用下， 以 四氢呋喃 为溶剂， 以77.7%的产率得到S_s-2-methyl-propane-2-sulfinic acid [3-methyl-butylidene]amide
  参考文献：
  名称：

  用于制备手性胺的手性 N-叔丁基亚磺酰基二亚胺的有机镁和有机锂试剂之间的逆转非对映选择性

  摘要：

  摘要 通过非对映选择性加成简单地改变有机金属试剂，从 N-叔丁基亚磺酰基醛亚胺 (3) 的单一手性来源不对称合成两种手性胺的对映异构体。报告了一种有效的对映选择性合成手性胺，包括 (S)-3-甲基-1-(2-哌啶-1-基-苯基) 丁胺 (6a)，这是制备抗糖尿病药物瑞格列奈 (1) 的关键中间体。图形概要

  DOI：

  10.1080/00397911.2014.909487

文献信息

• Reversal Diastereoselectivity Between the Organomagnesium and Organolithium Reagents on Chiral <i>N</i>-<i>Tert</i>-Butylsulfinylaldimines for the Preparation of Chiral Amines
  作者：Chinnapillai Rajendiran、Periyandi Nagarajan、A. Naidu、P. K. Dubey

  DOI：10.1080/00397911.2014.909487

  日期：2014.10.18

  Abstract The asymmetric synthesis of both the enantiomer of chiral amines from the single chiral source of N-tert-butylsulfinylaldimines (3) by simply changing the organometallic reagents through diastereoselective addition. An efficient enantioselective synthesis of chiral amines including (S)-3-methyl-1-(2-piperidin-1-yl-phenyl)butyl amine (6a), a key intermediate to prepare antidiabetic drug repaglinide

  摘要 通过非对映选择性加成简单地改变有机金属试剂，从 N-叔丁基亚磺酰基醛亚胺 (3) 的单一手性来源不对称合成两种手性胺的对映异构体。报告了一种有效的对映选择性合成手性胺，包括 (S)-3-甲基-1-(2-哌啶-1-基-苯基) 丁胺 (6a)，这是制备抗糖尿病药物瑞格列奈 (1) 的关键中间体。图形概要
• Stereospecific Synthesis of Fluoroalkenes by Silver-Mediated Fluorination of Functionalized Alkenylstannanes
  作者：Heiko Sommer、Alois Fürstner

  DOI：10.1002/chem.201605444

  日期：2017.1.12

  sorts. Key to success is the use of F‐TEDA‐PF6 in combination with non‐hygroscopic and bench‐stable silver phosphinate (AgOP(O)Ph2) that acts as an essentially neutral, non‐nucleophilic promotor and effective tin‐scavenger at the same time. This new method opens many opportunities for late‐stage fluorination of elaborate compounds far beyond the scope of the literature procedures, as witnessed by the preparation

  已知的将链烯基锡烷转化为相应的氟代烯烃的方法的收率变化很大，并且与官能团的相容性有限。最值得注意的是，每当基质中存在质子位点时，原去锡碱化就成为一个严重的问题。本文概述了一种方便的替代方法，其应用程序已大大改进，几乎不受各种游离醇和酰胺的干扰。成功的关键是将F‐TEDA‐PF 6与不吸湿且稳定的次膦酸银（AgOP（O）Ph 2），同时起着中性，非亲核的促进剂和有效的除锡剂的作用。这种新方法为精细化合物的后期氟化开辟了许多机会，远远超出了文献程序的范围，如制备氟化大环内酯类抗生素，氟化前列腺素衍生物以及一组氟化氨基酸替代物和肽等排体所证明的那样。 。
• Stereoselective Addition of 2-Phenyloxazol-4-yl Trifluoromethanesulfonate to <i>N</i>-Sulfinyl Imines: Application to the Synthesis of the HCV Protease Inhibitor Boceprevir
  作者：William J. Morris、Kiran K. Muppalla、Cameron Cowden、Richard G. Ball

  DOI：10.1021/jo301856f

  日期：2013.1.18

  The stereoselective addition of 2-phenyloxazol-4-yl trifluoromethanesulfonate to N-sulfinylimines is described. Vinyl anions derived from enol triflate 2 undergo 1,2-addition with a variety of aldimines to afford the corresponding secondary sulfonamides as single diastereomers. The absolute stereochemistry was confirmed by X-ray crystallography which provides support that the reaction proceeds through

  描述了将2-苯基恶唑-4-基三氟甲磺酸盐立体选择性加成到N-亚磺酰亚胺中。衍生自烯醇三氟甲磺酸酯2的乙烯基阴离子与各种醛亚胺进行1,2-加成反应，得到相应的仲磺酰胺，为单一非对映异构体。X射线晶体学证实了绝对立体化学，这提供了反应通过开放的，非螯合的过渡态进行的支持。该方法已经应用于蛋白酶抑制剂博西普韦的酮酰胺片段的合成。
• Peptidotriazolamers Inhibit Aβ(1–42) Oligomerization and Cross a Blood‐Brain‐Barrier Model
  作者：Nicolo Tonali、Loreen Hericks、David C. Schröder、Oliver Kracker、Radosław Krzemieniecki、Julia Kaffy、Vadim Le Joncour、Pirjo Laakkonen、Antoine Marion、Sandrine Ongeri、Veronica I. Dodero、Norbert Sewald

  DOI：10.1002/cplu.202000814

  日期：2021.6

  G39VVIA42 in Aβ(1–42). We found that peptidotriazolamers act as modulators of the Aβ(1–42) oligomerization. Some peptidotriazolamers are able to interfere with the formation of toxic early Aβ oligomers, depending on the position of the triazoles, which is also supported by computational studies. Preliminary in vitro results demonstrate that a highly active peptidotriazolamer is also able to cross the blood-brain-barrier

  在肽三唑仑中，每隔一个肽键被 1 H -1,2,3-三唑取代。这种折叠体有望弥合小分子药物和基于蛋白质的药物之间的分子量差距。淀粉样蛋白 β (Aβ) 聚集体在阿尔茨海默病中起重要作用。我们研究了 1,4-二取代的 1 H -1,2,3-三唑取代酰胺键对聚集“热点”K 16 LVFF 20和 G 39 VVIA 42抑制活性的影响在 Aβ(1-42) 中。我们发现肽三唑仑可作为 Aβ(1-42) 寡聚化的调节剂。一些肽三唑仑能够干扰有毒的早期 Aβ 低聚物的形成，这取决于三唑的位置，这也得到了计算研究的支持。初步体外结果表明，高活性肽三唑仑也能够穿过血脑屏障。
• 2,4-Disubstituted Thiazoles by Regioselective Cross-Coupling or Bromine-Magnesium Exchange Reactions of 2,4-Dibromothiazole
  作者：Thorsten Bach、Stefan Gross、Stefan Heuser、Carolin Ammer、Golo Heckmann

  DOI：10.1055/s-0030-1258373

  日期：2011.1

  Cross-coupling reactions occur on 2,4-dibromothiazole preferentially at the more electron-deficient 2-position. This fact can be favorably used to prepare 2-substituted 4-bromothiazoles, which serve as precursors for 2,4-disubstituted thiazoles. Protocols for regioselective Negishi and Stille cross-coupling reactions are provided. Alternatively, the title compound can be metalated in 2-position by a halogen-metal exchange reaction. As a supplement to the well-established bromine-lithium exchange, the regioselective bromine-magnesium exchange reaction is presented.

  2,4-二溴噻唑的交叉偶联反应优先发生在更缺电子的 2 位。这一事实可用于制备 2-取代的 4-溴噻唑，作为 2,4-二取代噻唑的前体。本研究提供了区域选择性 Negishi 和 Stille 交叉偶联反应的方案。另外，还可以通过卤素-金属交换反应将标题化合物 2 位金属化。作为对成熟的溴-锂交换反应的补充，介绍了具有区域选择性的溴-镁交换反应。