N-Cbz-triphenyliminophosphorane | 81357-08-6

• 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: N-Cbz-triphenyliminophosphorane
• 英文别名: benzyl (triphenyl-λ⁵-phosphanylidene)carbamate；(Phenylmethyl) (triphenylphosphoranylidene)carbamate；benzyl N-(triphenyl-λ5-phosphanylidene)carbamate
• CAS: 81357-08-6
• 化学式: C₂₆H₂₂NO₂P
• 分子量: 411.44
• InChiKey: AOTVRJMMNFRFAI-UHFFFAOYSA-N

物化性质

• 沸点：
  559.6±43.0 °C(Predicted)
• 密度：
  1.12±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.6
• 重原子数：
  30
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.04
• 拓扑面积：
  38.7
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-Cbz-triphenyliminophosphorane 在 ruthenium(IV) oxide 、 sodium tetrahydroborate 、 sodium periodate 作用下， 以 四氢呋喃 、 水 、 丙酮 、 苯 为溶剂， 反应 24.0h， 生成 (-)-(2R)-N-benzyloxycarbonyl-3,3,3-trifluoroalanine
  参考文献：
  名称：

  New Versatile Fluorinated Chiral Building Blocks:  Synthesis and Reactivity of Optically Pure α-(Fluoroalkyl)-β-sulfinylenamines

  摘要：

  Efficient synthesis of optically pure alpha-(fluoroalkyl)-beta-sulfinyl enamines has been achieved by aza-Wittig reaction of triphenyliminophosphoranes with the corresponding alpha-fluorinated-alpha'-sulfinyl ketones. The title compounds 3,4 showed an overwhelming preference for the Z stereochemistry of the enamine form. Their general reactivity has been studied. The reaction with some electrophiles (i.e. benzyl chloroformate and benzyl and allyl bromide) occurs at the nitrogen atom providing the corresponding N,N-disubstituted enamines. Nucleophiles add smoothly to C-2: heteroatom-centered nucleophiles like methanol, ammonia, and thiophenol afford gem-disubstituted derivatives under thermodynamic control, while a C-centered nucleophile like nitromethane adds in irreversible fashion. The hydride- and deuteride-promoted reduction of 3,4 to the N-Cbz-protected (14) and N-unprotected (15) alpha-fluorinated-alpha'-sulfinyl amines has been studied. Hydride addition was stereoselective, while low stereoselection was obtained with the other tested nucleophiles. Desulfurization of the optically pure 1,1,1-trifluoro-3-sulfinyl amine 15a afforded (R)-1-(trifluoromethyl)ethylamine 17. The Pummerer rearrangement of 14 occurs in an unusual nonoxidative way affording the sulfenamide 24, that readily provided (R)-(2-H)- and -(2-D)-3,3,3-trifluoroalaninol (19) and (R)-3,3,3-trifluoroalanine (22).

  DOI：

  10.1021/jo952097r
• 作为产物：
  描述：

  肼基甲酸苄酯 在 溶剂黄146 、 sodium nitrite 作用下， 以 乙醚 、 水 为溶剂， 生成 N-Cbz-triphenyliminophosphorane
  参考文献：
  名称：

  1-氟-1-硝基（苯磺酰基）甲烷对映异构衍生的酮亚胺的对映选择性加成。

  摘要：

  开发了不对称的有机催化的氟化苯磺酰基硝基甲烷到伊斯丁衍生的酮亚胺。该反应被手性叔胺辛可宁有效地催化。这种方法学提供了一种新型的光学活性化合物，具有两个相邻的季碳立体中心，具有良好的收率（高达96％），适度的非对映选择性（高达5.7：1 dr）和出色的对映选择性（高达98/96％ee）。

  DOI：

  10.1039/c7ob02408h

文献信息

• Organocatalytic Asymmetric Dearomatization Reaction for the Synthesis of Axial Chiral Allene-Derived Naphthalenones Bearing Quaternary Stereocenters
  作者：Alemayehu Gashaw Woldegiorgis、Zhao Han、Xufeng Lin

  DOI：10.1021/acs.orglett.1c01849

  日期：2021.9.3

  γ-alkynyl-α-imino esters with complete atom economy is disclosed via chiral phosphoric acid catalysis. This protocol provides facile and efficient access to asymmetric construction of a broad range of axially chiral allene-derived naphthalenones bearing quaternary stereocenters in good yields with high diastereoselectivities and enantioselectivities.

  通过手性磷酸催化，公开了具有完全原子经济性的 1-取代 2-萘酚和 β,γ-炔基-α-亚氨基酯的高度区域选择性、非对映选择性和对映选择性脱芳构化反应。该协议提供了对广泛的轴向手性丙二烯衍生的萘酮的不对称构建的方便和有效的访问，这些萘酮具有良好的收率，具有高非对映选择性和对映选择性。
• Chiral Phosphoric Acid‐Catalyzed Enantioselective Synthesis of Pyrazole‐Based Unnatural α‐Amino Acid Derivatives
  作者：Alemayehu Gashaw Woldegiorgis、Zhao Han、Xufeng Lin

  DOI：10.1002/adsc.202101011

  日期：2022.1.18

  An enantioselective synthesis of unnatural pyrazole-based α-chiral amino acid derivatives from the asymmetric reaction of N-aryl-5-aminopyrazoles with β,γ-alkynyl-α-imino esters using a chiral spirocyclic phosphoric acid catalyst was developed. Using the established methodology, various pyrazole-based α-amino acid derivatives with tetrasubstituted carbon stereocenters were obtained in 67–98% yields

  使用手性螺环磷酸催化剂，通过N-芳基-5-氨基吡唑与 β,γ-炔基-α-亚氨基酯的不对称反应，开发了非天然吡唑基 α-手性氨基酸衍生物的对映选择性合成。使用已建立的方法，以 67-98% 的产率和 73-99% 的对映选择性获得了各种具有四取代碳立构中心的吡唑基 α-氨基酸衍生物。相应产物中的 NH 2官能团能够进一步转化为手性硫脲和内酰胺。
• Optically Active Aromatic and Heteroaromatic α-Amino Acids by a One-Pot Catalytic Enantioselective Addition of Aromatic and Heteroaromatic C−H Bonds to α-Imino Esters
  作者：Steen Saaby、Pau Bayón、Pompiliu S. Aburel、Karl Anker Jørgensen

  DOI：10.1021/jo0256787

  日期：2002.6.1

  procedure for the synthesis of non-natural aromatic and heteroaromatic alpha-amino acids is reported. Starting from readily available starting materials and application of a chiral BINAP-Cu(I) catalyst, the optically active products are formed with readily removable N-protecting groups. The scope of the reaction is demonstrated by the addition of substituted furans, thiophenes, pyrroles, and aromatic compounds

  报道了一种用于合成非天然芳族和杂芳族α-氨基酸的实用的一锅催化对映选择性方法的开发。从容易获得的起始原料和手性BINAP-Cu（I）催化剂的应用开始，形成具有易于除去的N-保护基的旋光产物。通过以高收率向N-烷氧基羰基-α-亚氨基酯中添加取代的呋喃，噻吩，吡咯和芳香族化合物来证明反应的范围，对呋喃的对映选择性高达96％ee，对呋喃的对映选择性高达93％ee。噻吩，98％为芳香族化合物。保护基易于除去，并且证明了芳族和杂芳族α-氨基酸的各种转化。
• Direct Catalytic Asymmetric Vinylogous Additions of α,β‐ and β,γ‐Butenolides to Polyfluorinated Alkynyl Ketimines
  作者：Barry M. Trost、Chao‐I. (Joey) Hung、Manuel J. Scharf

  DOI：10.1002/anie.201806249

  日期：2018.8.27

  We report a Zn‐ProPhenol catalyzed asymmetric Mannich reaction between butenolides and polyfluorinated alkynyl ketimines to obtain vinylogous products featuring two contiguous tetrasubstituted stereogenic centers. Notably, this is the first successful use of ketimines in the ProPhenol Mannich process, and the reaction offers a new approach for the preparation of pharmaceutically relevant products possessing

  我们报告了丁烯内酯与多氟炔基酮亚胺之间的Zn-ProPhenol催化的不对称曼尼希反应，以获得具有两个连续的四取代立体异构中心的乙烯基产物。值得注意的是，这是酮亚胺在ProPhenol Mannich工艺中的首次成功使用，该反应为制备具有三氟甲基化四取代烷基胺的药物相关产品提供了一种新方法。该反应可以在不影响催化剂效率的情况下大规模地进行，催化剂负载减少。而且，乙炔部分可以使用各种方法进一步加工。
• Synthesis of optically pure (R)- and (S)-α-trifluoromethyl-alanine
  作者：Pierfrancesco Bravo、Silvia Capelli、Stefano Valdo Meille、Fiorenza Viani、Matteo Zanda、Valery P. Kukhar、Vadim A. Soloshonok

  DOI：10.1016/s0957-4166(00)86276-x

  日期：1994.10

  (+)-(R)- and (-)-(S)-3,3,3-trifluoro-2-methyl-alanine (1) were synthesized from (+)-(R)-methyl-p-tolylsulphoxide (5) and N-alkoxycarbonylimino derivatives 4 of methyl 3,3,3-trifluoropyruvate (3). The absolute configuration was determined by X-ray analyses of two synthetic intermediates (2S,R(S))-6a and (2R,R(S))-6c.

  (+)-(R)-和(-)-(S)-3,3,3-三氟-2-甲基丙氨酸(1)是由(+)-(R)-甲基-p-甲苯基亚硫酸酯(5)和来自甲基3,3,3-三氟丙酮酸甲酯(3)的N-烷氧基甲酰亚胺衍生物(4)合成的。绝对构型通过两种合成中间体(2S,R(S))-6a和(2R,R(S))-6c的X射线分析确定。