diethyl (Z)-1-propenylphosphonate | 18689-36-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: diethyl (Z)-1-propenylphosphonate
• 英文别名: diethyl (prop-1(Z)-en-1-yl)phosphonate；Z-O,O-diethyl-prop-2-enylphosphonate；(Z) propenylphosphonate de diethyle；diethyl (Z)-prop-1-enylphosphonate；cis-Propen-(1)-yl-phosphonsaeure-diethylester；Diethyl-cis-propenyl-1-phosphonat；(Z)-1-diethoxyphosphorylprop-1-ene
• CAS: 18689-36-6
• 化学式: C₇H₁₅O₃P
• 分子量: 178.168
• InChiKey: VBHYLCOEVPIQKH-DAXSKMNVSA-N

物化性质

• 沸点：
  120 °C(Press: 2 Torr)
• 密度：
  1.020±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  11
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  diethyl (Z)-1-propenylphosphonate 在 四(三苯基膦)钯 溴 作用下， 以 四氯化碳 、 乙二醇二甲醚 为溶剂， 反应 10.0h， 生成 diethyl (E)-1-phenyl-1-propenylphosphonate
  参考文献：
  名称：

  α-溴烯基膦酸酯与芳基硼酸和烯基硼酸酯的偶联反应。

  摘要：

  [反应：见正文]用有机硼烷和-硼酸盐研究了过渡金属催化的α-溴代烯基膦酸酯的芳基化和烯基化。用芳基硼酸和钯催化剂成功进行了芳基化反应，而发现烯基硼酸酯和镍催化剂进行了烯基化反应。另外，通过烯基化制备的二烯的分子内Diels-Alder反应得到相应的加合物。

  DOI：

  10.1021/ol020167s
• 作为产物：
  描述：

  二乙基(苯基硫代甲基)磷酸酯 在 正丁基锂 、 间氯过氧苯甲酸 作用下， 反应 4.83h， 生成 diethyl (Z)-1-propenylphosphonate
  参考文献：
  名称：

  1-烯烃膦酸二乙酯的简便合成

  摘要：

  DOI：

  10.1055/s-1982-29994

文献信息

• [EN] PROCESS FOR THE PREPARATION OF ENANTIOMERICALLY ENRICHED COMPOUNDS<br/>[FR] PROCEDE DE PREPARATION DE COMPOSES ENRICHIS EN ENANTIOMERES
  申请人：DSM IP ASSETS BV

  公开号：WO2003099745A1

  公开（公告）日：2003-12-04

  Process for the preparation of enantiomerically enriched compounds with Formula Ar-C(R1)-C(R2)-Z wherein Ar represents an optionally substituted (hetero)aryl group, R1 and R2, each independently, represent H, an alkyl, (hetero)aryl, dialkylamino, amido, thioether, alkoxy or aryloxy group with the proviso that not both R1 and R2 represent H, or R1 and R2 form together with the C-atoms to which they are bound a (hetero)alkyl or (hetero) alkenyl ring and Z represents an electron withdrawing group, in which process a boronic acid derivate of Formula Ar-B(OR3)OR4 or its anhydride, wherein Ar is as described above and R3 and R4, each independently, represent H or an alkyl group, is reacted with an olefinic unsaturated compound with Formula R2 - C = C - (R1)Z, wherein R1, R2 and Z are as described above, in the presence of a transition metal catalyst comprising a transition metal chosen from Cu and group VIII of the Periodic Table and an enantiomerically enriched ligand L, having the Formula (I) where Cn together with the two O-atoms and the P-atom forms a substituted or non-substituted ring with 2-6 C-atoms, R5 and R6 each independently stand for H, an optionally substituted alkyl, aryl, alkaryl, or aralkyl group, or represent the group with Formula (II) wherein Cn1 may have the same meanings as given for Cn and B represents a bridging group, or R5 and R6 may form a heterocyclic ring together with the N-atom to which they are bound.

  制备具有Ar-C(R1)-C(R2)-Z式的对映富集化合物的过程，其中Ar代表可选择取代的(杂)芳基团，R1和R2分别独立地代表H、烷基、(杂)芳基、二烷基氨基、酰胺、硫醚、烷氧基或芳氧基团，但R1和R2不同时代表H，或者R1和R2与它们结合的C原子一起形成(杂)烷基或(杂)烯基环，Z代表一个电子吸引基团，在该过程中，以Formula Ar-B(OR3)OR4或其酐的硼酸衍生物为反应物，其中Ar如上所述，R3和R4分别独立地代表H或烷基团，与Formula R2 - C = C - (R1)Z的烯烃不饱和化合物反应，其中R1、R2和Z如上所述，在Cu和周期表第VIII族的过渡金属选择的过渡金属催化剂存在下，以对映富集的配体L为特征，其具有Formula (I)，其中Cn与两个氧原子和磷原子一起形成具有2-6个C原子的取代或非取代环，R5和R6分别独立地代表H、可选择取代的烷基、芳基、烷芳基或芳基基团，或代表具有Formula (II)的基团，其中Cn1可能具有与Cn相同的含义，B代表一个桥联基团，或者R5和R6可以与它们结合的N原子一起形成一个杂环。
• Process for the preparation of enantiomerically enriched compounds
  申请人：DSM IP Assets B.V.

  公开号：EP1364932A1

  公开（公告）日：2003-11-26

  Process for the preparation of enantiomerically enriched compounds with formula Ar - C(R1) - C(R2) - Z wherein Ar represents an optionally substituted (hetero)aryl group, R1 and R2, each independen tly, represent H, an alkyl, (hetero)aryl, dialkylamino, amido, thioether, alkoxy or aryloxy group with the proviso that not both R1 and R2 represent H, or R1 and R2 form together with the C-atoms to which they are bound a (hetero)alkyl or (hetero) alkenyl ring and Z represents an electron withdrawing group, in which process a boronic acid derivate of formula Ar - B(OR3)OR4 or its anhydride, wherein Ar is as described above and R3 and R4, each independently, represent H or an alkyl group, is reacted with an olefinic unsaturated compound with formula R2 - C = C - (R1)Z, wherein R1, R2 and Z are as described above, in the presence of a transition metal catalyst comprising a transition metal chosen from Cu and group VIII of the Periodic Table and an enantiomerically enriched ligand L, having the formula (I) where Cn together with the two O-atoms and the P-atom forms a substituted or non-substituted ring with 2-6 C-atoms, R5 and R6 each independently stand for H, an optionally substituted alkyl, aryl, alkaryl or aralkyl group, or represent the group with formula (II) wherein Cn1 may have the same meanings as given for Cn and B represents a bridging group, or R5 and R6 may form a heterocyclic ring together with the N-atom to which they are bound.

  制备具有Ar - C(R1) - C(R2) - Z式的对映体富集化合物的过程，其中Ar代表可选择取代的(杂)芳基团，R1和R2分别独立地代表H、烷基、(杂)芳基、二烷基氨基、酰胺、硫醚、烷氧基或芳基氧基团，但R1和R2不同时代表H，或者R1和R2与它们结合的C原子一起形成(杂)烷基或(杂)烯基环，Z代表一个电子吸引基团，在该过程中，Ar - B(OR3)OR4式的硼酸衍生物或其酐，其中Ar如上所述，R3和R4分别独立地代表H或烷基团，与具有R2 - C = C - (R1)Z式的烯烃不饱和化合物反应，其中R1、R2和Z如上所述，在Cu和周期表第VIII族中选择的过渡金属和具有式(I)的对映体富集配体L的存在下进行，其中Cn与两个氧原子和磷原子一起形成具有2-6个C原子的取代或非取代环，R5和R6分别独立地代表H、可选择取代的烷基、芳基、烷基芳基或芳基烷基团，或代表具有式(II)的团，其中Cn1可能具有与Cn给定的相同含义，B代表一个桥联基团，或者R5和R6可以与它们结合的N原子一起形成一个杂环。
• Microwave-Assisted Palladium-Catalyzed Cross-Coupling of Aryl and Vinyl Halides with H-Phosphonate Diesters
  作者：Marcin Kalek、Asraa Ziadi、Jacek Stawinski

  DOI：10.1021/ol801935r

  日期：2008.10.16

  bond was developed. Using a prevalent palladium catalyst, Pd(PPh3)4, a quantitative cross-coupling of various H-phosphonate diesters with aryl and vinyl halides was achieved in less than 10 min. The reactions occurred with retention of configuration at the phosphorus center and in the vinyl moiety. Using this protocol, several C-phosphonates, including those bearing nucleoside and cholesteryl moieties

  开发了一种微波辅助CP键形成的通用有效方法。使用一种流行的钯催化剂Pd（PPh3）4，在不到10分钟的时间内即可实现各种H-膦酸酯二酯与芳基卤化物和乙烯基卤化物的定量交叉偶联。在磷中心和乙烯基部分保留构型的情况下发生反应。使用该方案，可以高收率制备数种C-膦酸酯，包括带有核苷和胆固醇基部分的C-膦酸酯。
• Palladium-catalyzed New Carbon-Phosphorus Bond Formation
  作者：Toshikazu Hirao、Toshio Masunaga、Naoto Yamada、Yoshiki Ohshiro、Toshio Agawa

  DOI：10.1246/bcsj.55.909

  日期：1982.3

  Dialkyl arylphosphonates are prepared by the palladium-catalyzed reaction of aryl bromides with dialkyl phosphite in the presence of triethylamine. The similar treatment of vinyl bromides gives dialkyl vinylphosphonates stereoselectively.

  二烷基芳基膦酸酯是在三乙胺存在下通过芳基溴化物与亚磷酸二烷基酯的钯催化反应制备的。乙烯基溴化物的类似处理可立体选择性地得到乙烯基膦酸二烷基酯。
• Enantiospecific synthesis of 2-amino-3-methyl-4-phosphonobutanoic acids via 14-addition of lithiated Schöllkopf anion to prop-2-enylphosphonates
  作者：Vicente Ojea、María Ruiz、Gideon Shapiro、Esteban Pombo-Villar

  DOI：10.1016/s0040-4039(00)76883-3

  日期：1994.5

  High diastereoselectivity in the conjugate addition of lithiated Schöllkopf's bislactim ethers to E- and Z- prop-2-enylphosphonates was utilized to achieve a direct asymmetric synthesis of all four diastereoisomers of 2-amino-3-methyl-4-phosphonobutanoic acid, i.e. (+)-(2S, 3R)-4a, (+)-(2S, 3S)-4b and their corresponding enantiomers. Their relative configuration was definitively assigned from an NMR

  将锂化的Schöllkopf的双内酯醚共轭加成到E-和Z-丙-2-烯基膦酸酯中的非对映异构体选择性高，可实现2-氨基-3-甲基-4-膦酰基丁酸的所有四个非对映异构体的直接不对称合成，即（ +）-（2 S，3 R）-4a，（+）-（2 S，3 S）-4b及其对应的对映异构体。根据两种非对映异构体的氧杂膦烷衍生物的NMR研究确定了它们的相对构型。