2-chloro-(4R,5R)-bis[(1R,2S,5R)-menth-1-yloxycarbonyl]-1,3,2-dioxaphospholane | 1026023-96-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 2-chloro-(4R,5R)-bis[(1R,2S,5R)-menth-1-yloxycarbonyl]-1,3,2-dioxaphospholane
• 英文别名: (4R,5R)-bis((1R,2S,5R)-2-isopropyl-5-methylcyclohexyl) 2-chloro-1,3,2-dioxaphospholane-4,5-dicarboxylate；2-chloro-(4R,5R)-bis{[(1R,2S,5R)-2-isopropyl-5-methylcyclohex-1-yl]oxycarbonyl}-1,3,2-dioxaphospholane；bis[(1R,2S,5R)-5-methyl-2-propan-2-ylcyclohexyl] (4R,5R)-2-chloro-1,3,2-dioxaphospholane-4,5-dicarboxylate
• CAS: 1026023-96-0
• 化学式: C₂₄H₄₀ClO₆P
• 分子量: 491.005
• InChiKey: ZRCROIIUJPCTRH-NBWOUMIXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.5
• 重原子数：
  32
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  芳樟醇 、 2-chloro-(4R,5R)-bis[(1R,2S,5R)-menth-1-yloxycarbonyl]-1,3,2-dioxaphospholane 在 三乙胺 作用下， 以 四氢呋喃 、 氘代氯仿 为溶剂， 生成
  参考文献：
  名称：

  三氯化磷和酒石酸萜烯酯的衍生剂，用于测定醇的对映体纯度

  摘要：

  由C 2对称的酒石酸薄荷酯，降冰片基或富烯基酯和三氯化磷制备的杂环亚磷酸氯是廉价的衍生试剂，用于通过磷NMR测定醇的对映体纯度。从这项研究中鉴定出的最通用的试剂是，（1 R，2 S，5 R）-薄荷基（R，R）-酒石酸衍生的2-氯-1,3,2-二氧杂膦烷，经手性醇酯化后得到，显示出在0.1 ppm至1.5 ppm之间的磷NMR位移分散的非对映异构体亚磷酸酯。

  DOI：

  10.1016/j.tetasy.2011.04.004
• 作为产物：
  描述：

  (+)-(R,R)-Weinsaeure-di<(-)-(1R,2S,5R)-menthyl>ester 在 三氯化磷 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以87%的产率得到2-chloro-(4R,5R)-bis[(1R,2S,5R)-menth-1-yloxycarbonyl]-1,3,2-dioxaphospholane
  参考文献：
  名称：

  三氯化磷和酒石酸萜烯酯的衍生剂，用于测定醇的对映体纯度

  摘要：

  由C 2对称的酒石酸薄荷酯，降冰片基或富烯基酯和三氯化磷制备的杂环亚磷酸氯是廉价的衍生试剂，用于通过磷NMR测定醇的对映体纯度。从这项研究中鉴定出的最通用的试剂是，（1 R，2 S，5 R）-薄荷基（R，R）-酒石酸衍生的2-氯-1,3,2-二氧杂膦烷，经手性醇酯化后得到，显示出在0.1 ppm至1.5 ppm之间的磷NMR位移分散的非对映异构体亚磷酸酯。

  DOI：

  10.1016/j.tetasy.2011.04.004

文献信息

• 2-Chloro-(4<i>R</i>,5<i>R</i>)-bis[(1<i>R</i>,2<i>S</i>,5<i>R</i>)-menth-1-yloxycarbonyl)]-1,3,2-dioxaphospholane: A Practical Chiral Pool-Derived Reagent for Determining Enantiomeric Purity of Alcohols
  作者：Matthias Amberg、Uwe Bergsträsser、Georg Stapf、Jens Hartung

  DOI：10.1021/jo7026068

  日期：2008.5.1

  2-Chloro-(4R,5R)-bis[(1R,2S,5R)-menth-1-yloxycarbonyl)]-1,3,2-dioxaphospholane is a practical reagent for reliably determining enantiomeric purity of chiral alcohols via 31P NMR spectroscopy. The compound is available as a crystalline solid on a 20 g scale from PCl3 and bis[(1R,2S,5R)-menth-1-yl] tartrate. It is comparatively inert toward spontaneous hydrolysis under conventional laboratory conditions

  2-氯-（4 R，5 R）-双[（1 R，2 S，5 R）-薄荷基-1-基氧羰基）]-1,3,2-二氧磷杂环戊烷是一种可靠的试剂，可以可靠地确定对映体的纯度31 P NMR光谱法测定手性醇。该化合物可从PCl 3和酒石酸双[（（1 R，2 S，5 R）-薄荷基-1-基）]中以20 g规模的结晶固体形式获得。在常规实验室条件下，它对自发水解反应相对惰性，但是如果用手性醇处理，它会被醇盐定量地取代为氯化物。不等31非对映异构体2-烷氧基-1,3,2-二氧代膦酸酯的P NMR信号弥散约1.4-0.1 ppm。相关的积分比反映了（R）-和（S）-1-苯基乙醇，（+）-和（-）-薄荷醇以及一组伯，仲和叔醇的预加权样品的对映体纯度，精确度为±0.4–1.0％。
• cis-2,6-Bis-(methanolate)-piperidine oxovanadium(V) complexes as catalysts for oxidative alkenol cyclization by tert-butyl hydroperoxide
  作者：Maike Dönges、Matthias Amberg、Georg Stapf、Harald Kelm、Uwe Bergsträßer、Jens Hartung

  DOI：10.1016/j.ica.2014.02.007

  日期：2014.8

  cis-2,6-Bis-(methanolate)-piperidine oxovanadium(V) complexes are Lewis acids able to catalyze oxidative cyclization of alkenols by tert-butyl hydroperoxide (TBHP). Terminal dimethyl-substituted (prenyl-type) 4-pentenols bearing an alkyl or a phenyl group in position 1 afford under such conditions 2,5-cis-derivatives of 2-(tetrahydrofuran-2-yl)-2-propanol as major and tetrahydropyran-3-ols as minor products (four examples). Oxidizing 1-phenyl-6-methylhept-5-en-l-ol yields a 75125-mixture of the derived 2-(tetrahydropyran-2-yl)-2-propanol and an oxepan-3-ol, whereas 2-propenols give epoxides in up to 94% yield. Epoxidizing geraniol by TBHP in the presence of a vanadium catalyst prepared from (2,5,6R)-2-diphenylmethanol-6-hydroxymethylpiperidine occurs enantioselectively. Highfield shifts of vanadium-51 resonances upon adding alkyl hydroperoxides to solutions of cis-2,6-bis-(methanolate)-piperidine vanadium(V) complexes point to vanadium(V) tert-butyl peroxy complex formation as key step for activating peroxides. (C) 2014 Elsevier B.V. All rights reserved.
• A study on the stereoselectivity of C,O bond formation in esterification of cyclic thiohydroxamic acids
  作者：Jens Hartung、Irina Kempter、Thomas Gottwald、Michaela Schwarz、Rainer Kneuer

  DOI：10.1016/j.tetasy.2009.08.020

  日期：2009.9

  Esterification of cyclic thiohydroxamic acids, for example, N-hydroxypyridine-2(1H)-thione, N-hydroxy-4-metlylthiazole-2(3H)-thione, and N-hydroxy-4-(p-chloiophenyl)-thiazole-2(3H)-thione, occuried with inversion of configuration at the attacked stereocenter, as evident from the use of chiral alcohols, alkyl p-toluene sulfonates, and cyclic sulfates. Stereochemical analysis of enant omerically pure O-alkyl thiohydroxamates was performed on the basis of CD-spectroscopy and chemical derivatizition. The assignment of the relative configuration in cyclic O-esters was feasible via NMR spectroscopy, whereas chiral aliphatic glycolato monoesters required hydroxyl group derivatization with chloro-(4R,5R)bis[(1R,2S,5R)-menth-1-yloxycarbonyl)]-1,3,2-dioxaphospholane for this purpose. (C) 2009 Elsevier Ltd All rights reserved
• New chiral phosphite ligands bearing sp2-nitrogen: complexation properties and palladium(II)-catalysed enantioselective allylic alkylation
  作者：Alexei I. Polosukhin、Oleg G. Bondarev、Sergey E. Lyubimov、Andrei V. Korostylev、Konstantin A. Lyssenko、Vadim A. Davankov、Konstantin N. Gavrilov

  DOI：10.1016/s0957-4166(01)00382-2

  日期：2001.8

  New homochiral P,N-bidentate phosphite-type ligands containing sp(2)-nitrogen were synthesised and their complexation with Rh(I) and Pd(II) atoms was investigated. The X-ray crystal structure of one of the chelate chlorocarbonyl rhodium complexes was obtained. E.e.s of up to 85% were attained in the Pd-catalysed allylic substitution reaction using the new P,N-ligands. (C) 2001 Elsevier Science Ltd. All rights reserved.
• Derivatizing agents from phosphorus trichloride and terpenyl tartrates for determining the enantiomeric purity of alcohols
  作者：Matthias Amberg、Irina Kempter、Uwe Bergsträßer、Georg Stapf、Jens Hartung

  DOI：10.1016/j.tetasy.2011.04.004

  日期：2011.4

  Heterocyclic phosphorous acid chlorides, prepared from C2-symmetric menthyl, borneyl, or fenchyl tartrates and phosphorus trichloride, are inexpensive derivatizing agents for determining the enantiomeric purity of alcohols via phosphorus NMR. The most versatile agent identified from this study, a (1R,2S,5R)-menthyl (R,R)-tartrate-derived 2-chloro-1,3,2-dioxaphospholane, gives, upon esterification with

  由C 2对称的酒石酸薄荷酯，降冰片基或富烯基酯和三氯化磷制备的杂环亚磷酸氯是廉价的衍生试剂，用于通过磷NMR测定醇的对映体纯度。从这项研究中鉴定出的最通用的试剂是，（1 R，2 S，5 R）-薄荷基（R，R）-酒石酸衍生的2-氯-1,3,2-二氧杂膦烷，经手性醇酯化后得到，显示出在0.1 ppm至1.5 ppm之间的磷NMR位移分散的非对映异构体亚磷酸酯。