(S)-(-)-2-(1-methyl-allyl)malonic acid dimethyl ester | 92747-21-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (S)-(-)-2-(1-methyl-allyl)malonic acid dimethyl ester
• 英文别名: dimethyl 2-[(S)-1-methylprop-2-enyl]propanedioate；dimethyl 3-methyl-1-butene-4,4-dicarboxylate；dimethyl (S)-(+)-1-buten-3-ylmalonate；(S)-dimethyl (1-methylprop-2-enyl)malonate；dimethyl 2-[(2S)-but-3-en-2-yl]propanedioate
• CAS: 92747-21-2
• 化学式: C₉H₁₄O₄
• 分子量: 186.208
• InChiKey: RXGVYPLIBNAVDM-LURJTMIESA-N

物化性质

• 沸点：
  182.3±20.0 °C(Predicted)
• 密度：
  1.035±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  13
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (S)-(-)-2-(1-methyl-allyl)malonic acid dimethyl ester 在 水 、 氢气 作用下， 生成 (S)-3-甲基戊酸
  参考文献：
  名称：

  TRANSFER OF ASYMMETRY BY THE PALLADIUM-CATALYZED ALKYLATION OF CHIRAL ALLYLIC SULFINATES

  摘要：

  通过将手性烯丙基亚磺酸盐初步转化为烯丙基磺酸盐，并随后对磺酸盐进行保持构型的烷基化，进行了钯催化的取代反应。以反式和顺式2-丁烯基(S)-(−)-对甲苯磺酸盐与二甲基恶唑酸钠盐在四配位(triphenylphosphine)palladium和三苯基膦的存在下反应，分别生产出二甲基(S)-(+)-和(R)-(−)-1-丁-3-基恶唑酸酯，以及α-烷基化的产物：二甲基2-丁烯基恶唑酸酯。

  DOI：

  10.1246/cl.1984.929
• 作为产物：
  描述：

  二甲基丙二酸钠 、 (+)-(R)-but-3-en-2-yl acetate 在 bis(η3-allyl-μ-chloropalladium(II)) 三环己基膦 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 生成 dimethyl 2-((1R)-1-methylprop-2-enyl)propane-1,3-dioate 、 (S)-(-)-2-(1-methyl-allyl)malonic acid dimethyl ester
  参考文献：
  名称：

  区域选择性钯催化的烯丙基取代反应中的显着配体效应

  摘要：

  在钯催化的烯丙基取代反应中使用三环己基膦（及相关的膦）可以将支链烯丙基乙酸酯选择性转化为支链取代产物（区域选择性高达120：1）。线性烯丙基乙酸酯对支链取代产物没有显示出相同的选择性，从而表现出记忆效应。

  DOI：

  10.1002/1615-4169(20010129)343:1<75::aid-adsc75>3.0.co;2-w

文献信息

• Chiral Bis(N-sulfonylamino)phosphine- and TADDOL-Phosphite-Oxazoline Ligands: Synthesis and Application in Asymmetric Catalysis
  作者：Robert Hilgraf、Andreas Pfaltz

  DOI：10.1002/adsc.200404168

  日期：2005.1

  has been prepared, containing a chiral oxazoline ring and as a second chiral unit a bis(N-sulfonylamino)phosphine group embedded in a diazaphospholidine ring or a cyclic phosphite group derived from TADDOL. These modular ligands are readily synthesized from chiral amino alcohols and chiral 1,2-diamines or TADDOLs. Palladium and iridium complexes derived from these ligands were found to be efficient catalysts

  制备了一系列N，P-配体，其包含手性恶唑啉环和嵌入在二氮磷吡啶环中的双（N-磺酰基氨基）膦基或衍生自TADDOL的环状亚磷酸酯基作为第二手性单元。这些模块化配体易于从手性氨基醇和手性1,2-二胺或TADDOLs合成。发现衍生自这些配体的钯和铱配合物分别是对映选择性烯丙基烷基化和烯烃氢化的有效催化剂。
• Iridium-Catalysed Allylic Substitution: Stereochemical Aspects and Isolation of IrIII Complexes Related to the Catalytic Cycle
  作者：Björn Bartels、Cristina García-Yebra、Frank Rominger、Günter Helmchen

  DOI：10.1002/1099-0682(200210)2002:10<2569::aid-ejic2569>3.0.co;2-5

  日期：2002.10

  Ir-catalysed allylic alkylations of enantiomerically enriched monosubstituted allylic acetates proceed with up to 87% retention of configuration using P(OPh)3 as ligand. High regio- and enantioselectivity of up to 86% ee in asymmetric allylic alkylations of achiral or racemic substrates is achieved with monodentate phosphorus amidites as ligands. Lithium N-tosylbenzylamide was identified as a suitable

  使用 P(OPh)3 作为配体，Ir 催化的烯丙基烷基化对映体富集的单取代烯丙基乙酸酯的构型保留率高达 87%。以单齿磷酰胺作为配体，在非手性或外消旋底物的不对称烯丙基烷基化中实现了高达 86% ee 的高区域和对映选择性。N-tosylbenzylamide 锂被确定为适合烯丙基胺化的亲核试剂。特别重要的是使用氯化锂作为添加剂，通常会导致对映选择性增加。通过 X 射线晶体结构分析和光谱数据对两种 (π-烯丙基) IrIII 配合物进行了表征。
• Chiral Bis(<i>N</i>-tosylamino)phosphine- and TADDOL-Phosphite-Oxazolines as Ligands in Asymmetric Catalysis
  作者：Robert Hilgraf、Andreas Pfaltz

  DOI：10.1055/s-1999-2939

  日期：1999.11

  A series of P,N-ligands containing a chiral oxazoline ring and a chiral bis(N-tosylamino)phosphine group derived from a 1,2-diamine or a chiral cyclic phosphite group derived from TADDOL has been prepared. These compounds proved to be efficient ligands for enantiocontrol of palladium-catalyzed allylic alkylations and iridium-catalyzed hydrogenations of olefins.

  一系列含手性噁唑啉环和手性双(N-甲苯磺酰氨基)膦基团（源自1,2-二胺）或手性环状亚磷酸酯基团（源自TADDOL）的P,N配体已被合成。这些化合物被证明是钯催化的烯丙基烷基化反应和铱催化的烯烃氢化反应中高效的手性控制配体。
• Synthesis of 1-[bis(trifluoromethyl)phosphine]-1’-oxazolinylferrocene ligands and their application in regio- and enantioselective Pd-catalyzed allylic alkylation of monosubstituted allyl substrates
  作者：Zeng-Wei Lai、Rong-Fei Yang、Ke-Yin Ye、Hongbin Sun、Shu-Li You

  DOI：10.3762/bjoc.10.126

  日期：——

  linylferrocene ligands has been synthesized from ferrocene. It became apparent that these ligands can be used in the regio- and enantioselective Pd-catalyzed allylic alkylation of monosubstituted allyl substrates in a highly efficient manner. Excellent regio- and enantioselectivity could be obtained for a wide range of substrates.

  已经从二茂铁合成了一类新型、易于获得且空气稳定的 1-[双（三氟甲基）膦]-1'-恶唑啉基二茂铁配体。很明显，这些配体可以高效地用于单取代烯丙基底物的区域选择性和对映选择性 Pd 催化的烯丙基烷基化。对于广泛的底物，可以获得优异的区域选择性和对映选择性。
• Highly Enantio- and Regioselective Allylic Alkylations Catalyzed by Chiral [Bis(dihydrooxazole)]molybdenum Complexes
  作者：Frank Glorius、Markus Neuburger、Andreas Pfaltz

  DOI：10.1002/1522-2675(20011017)84:10<3178::aid-hlca3178>3.0.co;2-q

  日期：2001.10.17

  A series of chiral C-2-symmetric bis[dihydrooxazoles] with a trans-1,2-diaminocyclohexane backbone was synthesized. In view of the promising results obtained by Trost et al with related bis[pyridine] ligands, we tested these new ligands in the enantioselective molybdenum-catalyzed allylic alkylation of 1- and 3-monosubstituted allylic substrates. Enantiomer excesses of up to 98% and branched/linear ratios of up to 11 : 1 were obtained with (E)-3-(alkyl)allyl carbonates. (E)-3-Phenoxyallyl acetate gave a branclied/linear ratio of > 20:1 and an ee of 98%. Crystal structures of the free ligand 7a and of its tricarbonylmolybdenum(0) complex 28 are reported.