(2S,5S,11aR)-1-(dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-yl)-2,5-diphenylpyrrolidine

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: (2S,5S,11aR)-1-(dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-yl)-2,5-diphenylpyrrolidine
• 英文别名: (11bS)-(2S,5S)-1-(Dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-yl)-2,5-diphenylpyrrolidine；(2S,5S)-1-(12,14-dioxa-13-phosphapentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3,5,7,9,16,18,20,22-decaen-13-yl)-2,5-diphenylpyrrolidine
• 化学式: C₃₆H₂₈NO₂P
• 分子量: 537.598
• InChiKey: SQEYSQAZYNQDSV-ACHIHNKUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.6
• 重原子数：
  40
• 可旋转键数：
  3
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  (R)-1,1'-Bi-2-naphthol 在 N-甲基吡咯烷酮 、 4-二甲氨基吡啶 、 三乙胺 、 三氯化磷 作用下， 以 甲苯 为溶剂， 反应 1.25h， 生成 (2S,5S,11aR)-1-(dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-yl)-2,5-diphenylpyrrolidine
  参考文献：
  名称：

  反式2,5-二芳基吡咯烷催化剂的Mukaiyama–Michael反应：有吸引力的非共价相互作用而非立体阻滞引起对映选择性

  摘要：

  反式2,5-二苯基吡咯烷催化的对映选择性Mukaiyama-Michael反应的范围已扩大到包括α-和β-取代的Enals。但是，由于催化剂的空间位阻不是很强，因此观察到的对映选择性的合理化还远远不够。进行DFT计算以合理化观察到的立体选择性。作为C过渡态定位亚胺中间体和甲硅烷氧基呋喃之间的C键形成，并用它们的相对能量估算立体选择性数据。我们在预测和观察到的立体选择性之间发现了极好的一致性。分子间力的分析表明，对映选择性主要是由于稳定了反应伙伴之间的非共价相互作用，而不是由于空间位阻。有吸引力的非共价相互作用在对映选择性催化中的作用可能未被充分认识。

  DOI：

  10.1002/chem.201304240
• 作为试剂：
  描述：

  methyl 5-methylene-2-oxo-3-phenyltetrahydro-2H-pyran-3-carboxylate 、 N-甲苯磺酰基氮杂环丙烷 在 allyl(cyclopentadiene)palladium(II) 、 (2S,5S,11aR)-1-(dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-yl)-2,5-diphenylpyrrolidine 作用下， 以 甲苯 为溶剂， 反应 24.08h， 生成 methyl (4R)-6-methylidene-1-(4-methylphenyl)sulfonyl-4-phenylazepane-4-carboxylate 、
  参考文献：
  名称：

  Palladium-Catalyzed Decarboxylative [4 + 3] Cyclization of γ-Methylidene-δ-valerolactones with 1,1-Dicyanocyclopropanes

  摘要：

  A palladium-catalyzed decarboxylative [4 + 3] cyclization of gamma-methylidene-delta-valerolactones with 1,1-dicyanocyclopropanes has been developed to produce cycloheptane derivatives in a convergent manner. This method can be applied to the synthesis of azepanes by reacting with aziridines, and their asymmetric variants have also been described. In addition, selective ring-expansion reactions can be achieved for certain gamma-methylidene-delta-valerolactones to give nondecarboxylated nine-membered lactones.

  DOI：

  10.1021/ol902326s

文献信息

• Asymmetric Synthesis of Enantiopure Pyrrolidines by C(sp ³ )−H Amination of Hydrocarbons
  作者：Yanis Lazib、Pascal Retailleau、Tanguy Saget、Benjamin Darses、Philippe Dauban

  DOI：10.1002/anie.202107898

  日期：2021.9.27

  asymmetric synthesis of enantiopure pyrrolidines is reported via a streamlined strategy relying on two sequential C−H functionalizations of simple hydrocarbons. The first step is a regio- and stereoselective catalytic nitrene C−H insertion. Then, a subsequent diastereoselective cyclization involving a 1,5-hydrogen atom transfer (HAT) from a N-centered radical leads to the formation of pyrrolidines that can

  对映体纯吡咯烷的不对称合成是通过依赖于简单烃的两个连续 CH 官能化的简化策略报道的。第一步是区域选择性和立体选择性催化氮烯 CH 插入。然后，随后的非对映选择性环化反应涉及来自 N 中心自由基的 1,5-氢原子转移 (HAT)，导致形成吡咯烷，然后可以将其转化为游离的 NH 衍生物。
• PHOSPHORAMIDITE LIGAND AND PRODUCTION METHOD OF ALLYLIC AMINE USING THE SAME
  申请人：CARREIRA Erick M.

  公开号：US20090054689A1

  公开（公告）日：2009-02-26

  The present invention provides a production method of an allylic amine represented by the formula (III): wherein R 3 is as defined in the specification, which comprises reacting by an allylic alcohol represented by the formula (II): wherein R 3 is as defined in the specification, with sulfamic acid, in the presence of a phosphoramidite ligand represented by the formula (I): wherein each symbol is as defined in the specification, and an iridium complex. According to the present invention, a primary allylic amine can be produced directly from an allylic alcohol, without use of an activator for an allylic alcohol and conversion of an allylic alcohol into an activated compound thereof.

  本发明提供了一种制备烯丙胺的生产方法，烯丙胺的化学式为(III)，其中R3如规范中定义，该方法包括使用磷酰胺配体(I)和铱配合物，在磺酸的存在下，将烯丙醇(II)与磺酸反应。根据本发明，可以直接从烯丙醇中生产出主要的烯丙胺，而无需使用烯丙醇的活化剂，也无需将烯丙醇转化为其活化化合物。
• 3,3,3',3'-TETRAMETHYL-1,1'-SPIROBIINDANE-BASED MONOPHOSPHINE LIGAND, INTERMEDATES TEHREOF, PREPARATION METHOD AND USE OF THE SAME
  申请人：ZHEJIANG UNIVERSITY

  公开号：US20210070789A1

  公开（公告）日：2021-03-11

  Provided are a 3,3,3′,3′-tetramethyl-1,1′-spirobiindane-based monophosphine ligand and intermediates thereof, and preparation methods and uses of the same. The monophosphine ligand is a compound represented by formula I or formula I′, or an enantiomer, a raceme or a diastereoisomer thereof, including phosphonite ligands, phosphite ligands, phosphoramidite ester ligands, phosphoric acid and phosphonic amide. The monophosphine ligand is prepared with a known 3,3,3′,3′-tetramethyl-1,1′-spirobiindane-7,7′-diol derivative as a raw material through a scheme in which the compound presented by formula II acts as an intermediate. The present disclosure provides a novel monophosphine ligand, which can be used as a ligand in a metal-catalysed organic reactions or in directly catalyzing an organic reaction, especially as a chiral monophosphine ligand widely used in many chiral catalytic reactions such as asymmetric addition, asymmetric hydrogenation, asymmetric coupling, and asymmetric allyl alkylation, having economic practicality and industrial application prospects.
• 3,3,3',3'-TETRAMETHYL-1,1'-SPIROBIINDANE-7,7'-DIOL
  申请人：ZHEJIANG UNIVERSITY

  公开号：US20220213015A1

  公开（公告）日：2022-07-07

  Provided herein is 3,3,3′,3′-tetramethyl-1,1′-spirobiindane-7,7′-diol, which is a compound represented by formula I, or an enantiomer or a raceme thereof. The 3,3,3′,3′-tetramethyl-1,1′-spirobiindane-7,7′-diol is prepared with a 3,3,3′,3′-tetramethyl-1,1′-spirobiindane-7,7′-dicarbaldehyde derivative as a starting material through a Baeyer-Villiger oxidation rearrangement reaction and an alkaline hydrolysis reaction. The 3,3,3′,3′-tetramethyl-1,1′-spirobiindane-7,7′-diol comprises two gem-dimethyl groups and is a key intermediate for preparing corresponding 3,3,3′,3′-tetramethyl-1,1′-spirobiindane-based monophosphine ligands, such as phosphonite ligands, phosphite ligands, phosphoramidite ester ligands, phosphoric acid and phsophonamidate. The 3,3,3′,3′-tetramethyl-1,1′-spirobiindane-7,7′-diol skeleton provided herein could be used in chemical industry and has economic practicality and industrial application prospects.
• US7863443B2
  申请人：——

  公开号：US7863443B2

  公开（公告）日：2011-01-04