(R,E)-2-methyl-N-(1-(naphthalen-2-yl)ethylidene)propane-2-sulfinamide

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (R,E)-2-methyl-N-(1-(naphthalen-2-yl)ethylidene)propane-2-sulfinamide
• 英文别名: (NE,R)-2-methyl-N-(1-naphthalen-2-ylethylidene)propane-2-sulfinamide
• 化学式: C₁₆H₁₉NOS
• 分子量: 273.399
• InChiKey: HGPNXFMEUVMVDN-XYSGSMRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 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：

  (R,E)-2-methyl-N-(1-(naphthalen-2-yl)ethylidene)propane-2-sulfinamide 在 盐酸 、 三甲基氯硅烷 、 二氯二茂锆 、 三乙胺 、 N,N-二异丙基乙胺 、 红铝 、 三氟乙酸 、 N-[(dimethylamino)-3-oxo-1H-1,2,3-triazolo[4,5-b]pyridin-1-yl-methylene]-N-methylmethanaminium hexafluorophosphate 、 锌 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 甲醇 、 二氯甲烷 、 甲苯 为溶剂， 反应 78.0h， 生成 (R)-4-(3-(3,5-Bis(trifluoromethyl)phenyl)thioureido)-3,3-dimethyl-5-oxo-5-(pyrrolidin-1-yl)pentyl 3-(3-((R)-3,3-dimethyl-1-((S)-2-methyl-2-(naphthalen-2-yl)pyrrolidin-1-yl)-1-oxobutan-2-yl)thioureido)-5-(trifluoromethyl)benzoate
  参考文献：
  名称：

  Stereospecific Furanosylations Catalyzed by Bis-thiourea Hydrogen-Bond Donors

  摘要：

  We report a new method for stereoselective O-furanosylation reactions promoted by a precisely tailored bis-thiourea hydrogen-bond-donor catalyst. Furanosyl donors outfitted with an anomeric dialkylphosphate leaving group undergo substitution with high anomeric selectivity, providing access to the challenging 1,2-cis substitution pattern with a range of alcohol acceptors. A variety of stereochemically distinct, benzyl-protected glycosyl donors were engaged successfully as substrates. Mechanistic studies support a stereospecific mechanism in which rate-determining substitution occurs from a catalyst-donor resting-state complex.

  DOI：

  10.1021/jacs.0c00335
• 作为产物：
  描述：

  2-萘乙酮 、 (R)-(+)-叔丁基亚磺酰胺 在 titanium(IV) tetraethanolate 作用下， 以 四氢呋喃 为溶剂， 以83%的产率得到(R,E)-2-methyl-N-(1-(naphthalen-2-yl)ethylidene)propane-2-sulfinamide
  参考文献：
  名称：

  在电荷加速的锍重排中部署亚磺胺可实现替代不对称曼尼希反应

  摘要：

  β-氨基酸衍生物是合成和生物化学中的关键结构元素。尽管作为制备它们的标志性方法，直接曼尼希反应在使用羧酸衍生物时遇到了重大挑战。事实上，化学选择性烯醇化物的形成不仅是一个陷阱（尤其是使用羧酰胺），而且最重要的是，无法通过烯醇化物/酮亚胺偶联可靠地获得 α-叔胺是这个百年反应的未解决问题。在此，我们报告了一种策略，使羧酰胺与酮亚胺首次直接偶联，用于非对映和对映选择性合成 β-氨基酰胺。这种概念上新颖的方法取决于对映体纯亚磺酰亚胺在锍重排中的创新部署，并立即解决了化学选择性问题，曼尼希过程的反应性和（相对和绝对）立体选择性。深入的计算研究解释了观察到的、意想不到的（非）立体选择性，并展示了分子内相互作用（包括伦敦分散）的关键作用，以准确描述反应机理。

  DOI：

  10.1021/jacs.2c05368

文献信息

• Cycloaddition of Chiral <i>tert</i>-Butanesulfinimines with Trimethylenemethane
  作者：George Procopiou、William Lewis、Gareth Harbottle、Robert A. Stockman

  DOI：10.1021/ol400720b

  日期：2013.4.19

  The cycloaddition of chiral tert-butanesulfinimines with trimethylenemethane is found to give facile access to methylene-pyrrolidines with good yields and diastereoselectivities. The full scope of the cycloaddition is explored, and a range of transformations of the formed methylenepyrrolidines to give a range of functionalized chiral pyrrolidines is presented.
• Synthesis of Enantiomerically Pure <i>N</i>-<i>tert</i>-Butanesulfinyl Imines (<i>tert</i>-Butanesulfinimines) by the Direct Condensation of <i>tert</i>-Butanesulfinamide with Aldehydes and Ketones
  作者：Guangcheng Liu、Derek A. Cogan、Timothy D. Owens、Tony P. Tang、Jonathan A. Ellman

  DOI：10.1021/jo982059i

  日期：1999.2.1

  Experimental details for the first general methods for the one-step preparation of N-tert-butanesulfinyl imines (tert-butanesulfinimines) (2) from aldehydes and ketones is described. To effect the condensations of tert-butanesulfinamide (1) with aldehydes, the Lewis acidic dehydrating agents MgSO4, CuSO4, or Ti(OEt)(4) are employed. Aldehyde condensations mediated by MgSO4 proceed in high yields (84-96%) when an excess of aldehyde is used. In contrast, only a slight excess of aldehyde (1.1 equiv) relative to tert-butanesulfinamide provides sulfinimines in high yields when the more Lewis acidic dehydrating agent CuSO4 is used. The CuSO4-mediated procedure is effective for a wide range of aldehydes, including sterically demanding aldehydes, such as isobutyraldehyde (90%), and electron-rich aldehydes, such as p-anisaldehyde (81%). The still more Lewis acidic Ti(OEt)(4) and Ti(O-i-Pr)(4) also afford N-tert-butanesulfinyl aldimines from especially unreactive aldehydes, such as pivaldehyde (82%). In addition, Ti(OEt)(4) is effective for the condensation of I with ketones to afford a wide range of N-tert-butanesulfinyl ketimines in good yields (77-91%). For sulfinyl ketimines derived from methyl or n-alkyl phenyl ketones and methyl or n-alkyl isopropyl ketones, only the E isomer is detected by H-1 and C-13 NMR in CDCl3. For those cases where the difference in steric demand about the imine is very small, such as for 2-hexanone, high E/Z ratios are still observed (5:1).
• Asymmetric Synthesis of 1,2-Diamines bearing Tetrasubstituted Centers from Nonstabilized Azomethine Ylides and <i>N</i>-Sulfinylketimines under Brønsted Acid Catalysis
  作者：Cristina Izquierdo、Francisco Esteban、José Luis García Ruano、Alberto Fraile、José Alemán

  DOI：10.1021/acs.orglett.5b03251

  日期：2016.1.4

  The first asymmetric cycloaddition of nonstabilized azomethine ylide and N-sulfinylimines is presented. In reactions with aryl-alkyl and heteroaryl-alkyl ketimines, excellent diastereoselectivities and good yields are obtained in all cases, regardless of the electronic character of the substituents at the aromatic rings. Moreover, the cycloadducts obtained can easily be deprotected in acid media, giving access to free 1,2-diamines which are prevalent in many natural and pharmaceutical products.