(3aR,7aR)-2-((3-bromobenzylidene)amino)-1,3-diisopropyloctahydrobenzo[d][1,3,2]diazaphosphole 2-oxide | 1281867-91-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (3aR,7aR)-2-((3-bromobenzylidene)amino)-1,3-diisopropyloctahydrobenzo[d][1,3,2]diazaphosphole 2-oxide
• CAS: 1281867-91-1
• 化学式: C₁₉H₂₉BrN₃OP
• 分子量: 426.337
• InChiKey: BHYYMEVRTUOVJT-RTBURBONSA-N

物化性质

• 沸点：
  490.6±47.0 °C(predicted)
• 密度：
  1.39±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.72
• 重原子数：
  25.0
• 可旋转键数：
  4.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.63
• 拓扑面积：
  35.91
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  丙烯酸苄酯 、 (3aR,7aR)-2-((3-bromobenzylidene)amino)-1,3-diisopropyloctahydrobenzo[d][1,3,2]diazaphosphole 2-oxide 在 二甲基苯基磷 作用下， 以 甲苯 为溶剂， 反应 120.0h， 以85%的产率得到benzyl 2-((S)-(3-bromophenyl)(((3aR,7aR)-1,3-diisopropyl-2-oxidohexahydro-1H-benzo[d][1,3,2]diazaphosphol-2(3H)-yl)amino)methyl)acrylate
  参考文献：
  名称：

  通过GAP化学/技术 ，手性N-膦酰基亚胺与丙烯酸酯的不对称aza-Morita-Baylis-Hillman反应†

  摘要：

  已证明手性N-膦酰基亚胺是在方便条件下与丙烯酸酯进行不对称氮杂-Morita-Baylis-Hillman（aza-MBH）反应的有效亲电子受体。以原子经济的方式，以高收率（高达99.4％）和非对映选择性（高达> 99：1 dr）生成了30个β-氨基丙烯酸酯实例。已证明该合成遵循GAP（基团辅助纯化）化学方法，即，无需使用色谱法或色谱法，只需用己烷/乙酸乙酯（v / v，10/1）洗涤粗产物即可简单地获得纯产物。重结晶。还进行了DFT计算，以支持考虑非对映选择性高的不对称诱导模型。

  DOI：

  10.1039/c6ob00847j
• 作为产物：
  描述：

  (3aR,7aR)-2-bromo-1,3-diisopropyloctahydrobenzo[d][1,3,2]diazaphosphole 2-oxide 在 titanium(IV) isopropylate 、 氨 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 12.0h， 生成 (3aR,7aR)-2-((3-bromobenzylidene)amino)-1,3-diisopropyloctahydrobenzo[d][1,3,2]diazaphosphole 2-oxide
  参考文献：
  名称：

  通过手性N-膦酰基亚胺的布朗斯台德酸催化的不对称氮杂-Baylis-Hillman反应合成非对映体富集的α-氨基甲基烯酮。

  摘要：

  报道了一种通过（R）-CSA催化的不对称氮杂-Baylis-Hillman反应制备α-氨基甲基烯酮的有效手性GAP方法。在温和的条件下和方便的GAP技术下可获得优异的收率和高非对映选择性。通过X射线衍射对N-膦酰基亚胺和手性烯胺酮的绝对构型的确认为GAP化学的手性机理提供了明确的解释。

  DOI：

  10.1002/asia.201901734

文献信息

• Group-Assisted Purification Chemistry for Asymmetric Mannich-type Reaction of Chiral <i>N</i>-Phosphonyl Imines with Azlactones Leading to Syntheses of α-Quaternary α,β-Diamino Acid Derivatives
  作者：Haowei Zhang、Zhen Yang、Brian Nlong Zhao、Guigen Li

  DOI：10.1021/acs.joc.7b02556

  日期：2018.1.19

  An asymmetric Mannich-type reaction between chiral N-phosphonyl imines and azlactones [oxazol-5(4H)-ones] has been established under convenient conditions at room temperature. The reaction was performed without using any bases, additives, or catalysts to achieve up to excellent chemical yields and diastereoselectivity for 32 examples. The α-quaternary syn-α,β-diamino acid products were purified simply

  在室温下方便的条件下，建立了手性N-膦酰基亚胺和a内酯[恶唑-5（4 H）-ones]之间的不对称曼尼希型反应。在不使用任何碱，添加剂或催化剂的情况下进行反应，以实现高达32个实例的优异的化学收率和非对映选择性。α-季顺-α，β二氨基酸产物简单地通过洗涤纯化，用助溶剂，粗混合物，继组辅助纯化化学/技术，而不涉及传统的色谱法或重结晶法。辅助部件可以很容易地取出并回收再利用。通过X射线结构分析明确分配了绝对构型。
• N,N-Diisopropyl-N-phosphonyl imines lead to efficient asymmetric synthesis of aziridine-2-carboxylic esters
  作者：Padmanabha V. Kattamuri、Yiwen Xiong、Yi Pan、Guigen Li

  DOI：10.1039/c3ob40251g

  日期：——

  Highly diastereoselective asymmetric synthesis of chiral aziridine-2-carboxylic esters is reported for 20 examples with good yields (51–87%) and excellent diastereoselectivities (>99 : 1 dr for most cases). The modified N-phosphonyl imines have proven to be superior to previous imine auxiliaries for the aza Darzens reaction by using a secondary isopropyl group to replace the primary benzyl group for

  据报道，手性氮丙啶-2-羧酸酯的高度非对映选择性不对称合成有 20 个实例，具有良好的产率（51-87%）和出色的非对映选择性（大多数情况下 >99:1 dr）。通过使用仲异丙基取代N , N的伯苄基，已证明改性N - 膦酰基亚胺在 aza Darzens 反应中优于以前的亚胺助剂。-二氨基保护。同时，发现在 4 Å 分子筛存在的情况下，在该温度下将预冷的亚胺溶液在 -78 °C 下缓慢加入到预先形成的 β-溴化烯醇锂混合物中的特殊操作对产率至关重要和非对映选择性。本方法可以提供对 β-羟基α-氨基酸和其他重要氨基构建块的简单和通用的访问。
• Asymmetric Carbamoyl Anion Additions to Chiral <i>N</i>-Phosphonyl Imines via the GAP Chemistry Process and Stereoselectivity Enrichments
  作者：Cole W. Seifert、Suresh Pindi、Guigen Li

  DOI：10.1021/jo5024443

  日期：2015.1.2

  Carbamoyl anions were found to smoothly react with chiral N-phosphonyl imines in toluene at -78 degrees C to r.t. using LiHMDS as the base. Group-assisted purification (GAP) has been utilized to give the pure amides without using column chromatography or recrystallization. The asymmetric reaction resulted in chiral N-phosphonyl amino amides with good to excellent yields (71-99%) and good crude diastereoselectivities (dr 84:16-95:5). In this GAP procedure, the crude solids are washed with diethyl ether to afford the pure products, as revealed by H-1 NMR analysis; GAP washing consistently increases the diastereopurity of the products, resulting in excellent diastereoselectivities, often with final dr > 99:1. Interestingly, the diastereoenriched products can be obtained either in the ether solution or as the suspended solid, depending on the substrate.
• Asymmetric Synthesis of α-Amino-1,3-dithianes via Chiral <i>N</i>-Phosphonyl Imine-Based Umpolung Reaction Without Using Chromatography and Recrystallization
  作者：Padmanabha V. Kattamuri、Teng Ai、Suresh Pindi、Yinwei Sun、Peng Gu、Min Shi、Guigen Li

  DOI：10.1021/jo200070d

  日期：2011.4.15

  A series of alpha-amino-1,3-dithianes have been synthesized via the asymmetric Umpolung reaction of 2-lithio-1,3-dithianes with chiral N-phosphonyl imines in good chemical yields (up to 82%) and good to excellent diastereoselectivities (>99:1). The manner by which chiral N-phosphonyl imines are slowly added into the solution of 2-lithio-1,3-dithiane was found to be crucial for achieving excellent diastereoselectivity. The current synthesis was proven to follow the GAP chemistry (group-assistant-purification chemistry) process, which avoids traditional purification techniques of chromatography or recrystallization, i.e., the pure chiral alpha-amino-1,3-dithianes attached with the chiral N-phosphonyl group were readily obtained by washing the solid crude products with hexane or a mixture of hexane ethyl acetate.