(1S,2R)-(-)-2-Methyl-1-[(1S)-methyl-3-oxopropyl]-3-[(4R)-isopropyl-2-oxazolidin-3-yl]-3-oxopropyl 2-(diphenylphosphanyl)benzoate | 206123-56-0

• 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: (1S,2R)-(-)-2-Methyl-1-[(1S)-methyl-3-oxopropyl]-3-[(4R)-isopropyl-2-oxazolidin-3-yl]-3-oxopropyl 2-(diphenylphosphanyl)benzoate
• 英文别名: [(2S,3S,4R)-2,4-dimethyl-1,6-dioxo-1-[(4R)-2-oxo-4-propan-2-yl-1,3-oxazolidin-3-yl]hexan-3-yl] 2-diphenylphosphanylbenzoate
• CAS: 206123-56-0
• 化学式: C₃₃H₃₆NO₆P
• 分子量: 573.626
• InChiKey: JDOBPXDOHQANCW-LASNWIGQSA-N

物化性质

• 沸点：
  703.0±60.0 °C(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 重原子数：
  41
• 可旋转键数：
  12
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  90
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (1S,2R)-(-)-2-Methyl-1-[(1S)-methyl-3-oxopropyl]-3-[(4R)-isopropyl-2-oxazolidin-3-yl]-3-oxopropyl 2-(diphenylphosphanyl)benzoate 在 copper(l) iodide 、 正丁基锂 作用下， 以 乙二醇二甲醚 、 乙醚 、 正己烷 为溶剂， 反应 2.17h， 生成 ethyl (3R,5R,6S,7S)-(-)-6-[2-(diphenylphosphanyl)benzoyloxy]-8-[(4R)-isopropyl-2-oxazolidin-3-yl]-3,5,7-trimethyloctanoate
  参考文献：
  名称：

  o -DPPB定向立体选择性共轭有机物。

  摘要：

  借助于与底物结合的指导o -DPPB-基团（o -DPPB =邻位-二苯基膦基苯甲酸酯）的试剂，已将Gilman铜酸盐的经底物定向的非对映选择性共轭加成到无环烯酸酯中。将o -DPPB定向的加氢甲酰化与o -DPPB定向的铜的加成反应相结合，可提供具有多达四个立体生成中心的结构单元，这可能与聚酮化合物的合成有关。报道了关于Gilman铜酸盐的邻-DPPB定向的铜酸盐的添加的限制和范围以及关于烯酸酯结构的控制以及探查邻-DPPB基团作用的对照实验。

  DOI：

  10.1016/s0040-4020(00)00139-3
• 作为产物：
  描述：

  2-二苯基膦苯甲酸 在 acetylacetonatodicarbonylrhodium(l) 亚磷酸三苯酯 、 4-二甲氨基吡啶 、 氢气 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 25.0~90.0 ℃ 、2.0 MPa 条件下， 反应 48.0h， 生成 (1S,2R)-(-)-2-Methyl-1-[(1S)-methyl-3-oxopropyl]-3-[(4R)-isopropyl-2-oxazolidin-3-yl]-3-oxopropyl 2-(diphenylphosphanyl)benzoate
  参考文献：
  名称：

  Substrate-Directed Diastereoselective Hydroformylation: Key Step for the Assembly of Polypropionate Subunits

  摘要：

  Stereoselective hydroformylation of methallylic alcohols of types 3 and 4, that employed the substrate-bound catalyst-directing ortho-diphenyl-phosphanylbenzoyl (o-DPPB) group, was used as a key step for the construction of bifunctionalized stereotriads, which ale central building blocks of polyketide natural products. The required diastereomerically pure syn- and anti- starting methallylic alcohol systems 3 and 4 were obtained either by Cram-selective carbonyl reduction, Frater alkylation, or by chelation-controlled carbonyl reduction. Enantiomerically pure stereotriad building blocks were derived from a combination of an Evans aldol addition and subsequent o-DPPB-directed stereoselective hydroformylation (-->24). A crystal structure analysis for steretriad building block 24 confirmed the relative and absolute configuration of the stereogenic centers. Additionally, it provided evidence for a previously postulated preferred conformation of the catalyst-directing o-DPPB group as well as of the polyketide main chain.

  DOI：

  10.1002/(sici)1521-3765(19991001)5:10<2819::aid-chem2819>3.0.co;2-z

文献信息

• ortho-Diphenylphosphanylbenzoyl-Directed Cuprate Addition to Acyclic Enoates
  作者：Bernhard Breit

  DOI：10.1002/(sici)1521-3773(19980302)37:4<525::aid-anie525>3.0.co;2-m

  日期：1998.3.2

  Killing two birds with one stone. The ortho-diphenylphosphanylbenzoyl group (o-DPPB) acts as a catalyst-directing group in stereoselective Rh-catalyzed hydroformylation and as a reagent-directing group in stereoselective 1,4-addition of Gilman cuprates to acyclic enoates (see picture on the right; the o-DPPB group is represented by a sphere, D=donor). These two reactions could be efficiently used as

  用一块石头杀死两只鸟。邻二苯基膦基苯甲酰基（o-DPPB）在立体选择性Rh催化的加氢甲酰化反应中充当催化剂导向基团，在吉尔曼铜酸盐向无环烯酸酯的立体选择性1,4-加成反应中用作试剂导向基团（见右图; o-DPPB基团由一个球体表示，D =施主。这两个反应可以有效地用作合成序列的一部分。
• Substrate-Directed Diastereoselective Hydroformylation: Key Step for the Assembly of Polypropionate Subunits
  作者：Bernhard Breit、Mario Dauber、Klaus Harms

  DOI：10.1002/(sici)1521-3765(19991001)5:10<2819::aid-chem2819>3.0.co;2-z

  日期：1999.10.1

  Stereoselective hydroformylation of methallylic alcohols of types 3 and 4, that employed the substrate-bound catalyst-directing ortho-diphenyl-phosphanylbenzoyl (o-DPPB) group, was used as a key step for the construction of bifunctionalized stereotriads, which ale central building blocks of polyketide natural products. The required diastereomerically pure syn- and anti- starting methallylic alcohol systems 3 and 4 were obtained either by Cram-selective carbonyl reduction, Frater alkylation, or by chelation-controlled carbonyl reduction. Enantiomerically pure stereotriad building blocks were derived from a combination of an Evans aldol addition and subsequent o-DPPB-directed stereoselective hydroformylation (-->24). A crystal structure analysis for steretriad building block 24 confirmed the relative and absolute configuration of the stereogenic centers. Additionally, it provided evidence for a previously postulated preferred conformation of the catalyst-directing o-DPPB group as well as of the polyketide main chain.
• o-DPPB-Directed Stereoselective Conjugate Addition of Organocuprates
  作者：Bernhard Breit、Peter Demel

  DOI：10.1016/s0040-4020(00)00139-3

  日期：2000.4

  Substrate-directed diastereoselective conjugate addition of Gilman cuprates to acyclic enoates has been achieved with the aid of the substrate-bound reagent-directing o-DPPB-group (o-DPPB=ortho-diphenylphosphanyl benzoate). Combining o-DPPB-directed hydroformylation with the o-DPPB-directed cuprate addition provides access to building blocks with up to four stereogenic centers, which may be of relevance

  借助于与底物结合的指导o -DPPB-基团（o -DPPB =邻位-二苯基膦基苯甲酸酯）的试剂，已将Gilman铜酸盐的经底物定向的非对映选择性共轭加成到无环烯酸酯中。将o -DPPB定向的加氢甲酰化与o -DPPB定向的铜的加成反应相结合，可提供具有多达四个立体生成中心的结构单元，这可能与聚酮化合物的合成有关。报道了关于Gilman铜酸盐的邻-DPPB定向的铜酸盐的添加的限制和范围以及关于烯酸酯结构的控制以及探查邻-DPPB基团作用的对照实验。