(R)-2,3-dihydro-1-phenyl-1H-phosphole 1-oxide | 171598-28-0

• 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: (R)-2,3-dihydro-1-phenyl-1H-phosphole 1-oxide
• 英文别名: (1R)-1-phenyl-2,3-dihydro-1lambda5-phosphole 1-oxide；(1R)-1-phenyl-2,3-dihydro-1λ5-phosphole 1-oxide
• CAS: 171598-28-0
• 化学式: C₁₀H₁₁OP
• 分子量: 178.171
• InChiKey: YUQUHJGNZFFDAA-LBPRGKRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (R)-2,3-dihydro-1-phenyl-1H-phosphole 1-oxide 、 (3S,4S)-3,4-di-tert-butoxy-1-pyrroline N-oxide 以 苯 为溶剂， 反应 12.0h， 以90%的产率得到(2S,3S,3aS,3bR,4R,6aR)-2,3-Di-tert-butoxy-4-phenyl-octahydro-1-oxa-7a-aza-4-phospha-cyclopenta[a]pentalene 4-oxide
  参考文献：
  名称：

  Asymmetric and Doubly Asymmetric 1,3-Dipolar Cycloadditons in the Synthesis of Enantiopure Organophosphorus Compounds

  摘要：

  DOI：

  10.1080/10426509908546263
• 作为产物：
  描述：

  苯基磷杂环戊-3-烯 在 potassium hydroxide 作用下， 以 1,4-二氧六环 、 水 为溶剂， 反应 16.0h， 生成 (R)-2,3-dihydro-1-phenyl-1H-phosphole 1-oxide
  参考文献：
  名称：

  铑催化氧化膦的不对称芳构化中的动态动力学拆分。

  摘要：

  在高碱性条件（10当量的KOH）下，在手性（R）-segphos-铑催化剂的存在下，2,5-二氢-1 H-磷化氢1-氧化物1与ArB（pin）3的反应产生了高收率高非对映选择性和高对映选择性的（1 S，3 S）-3-芳基膦烷1-氧化物4的合成。通过碱催化的烯烃异构化使1与2,3-二氢异构体2（手性和外消旋）平衡，然后用手性铑催化剂进行2的动力学拆分，实现了目前的动态动力学拆分。

  DOI：

  10.1021/jacs.7b04570

文献信息

• Kinetic Resolution in 1,3-Dipolar Cycloaddition of Tartaric Acid-Derived Nitrones to 2,3-Dihydro-1-phenyl-1H-phospholes. An Enantioselective Approach to the 2,2'-Coupled Pyrrolidine-Phospholane Ring System
  作者：Alberto Brandi、Stefano Cicchi、Andrea Goti、Marek Koprowski、K. Michal Pietrusiewicz

  DOI：10.1021/jo00085a019

  日期：1994.3

  Enantiomerically pure five-membered ring nitrones derived from L-tartaric acid via C2-symmetric O,O'-protected 3,4-dihydroxy pyrrolidines undergo highly regio- and stereoselective cycloaddition reactions with racemic 2,3-dihydro-1-phenyl-1H-phosphole 1-oxide and 1-sulfide. In all cases formation of only two diastereomeric cycloadducts is observed and their ratio (up to 10:1) is dependent on the size of the protecting groups in the nitrone and on the extent of conversion. The tricyclic cycloadducts feature 2,2'-connection of pyrrolidine and phospholane rings and six contiguous stereogenic centers of which three are created and the one at phosphorus is kinetically resolved during the cycloaddition process. It is established that in the studied kinetic resolutions the stereoselectivity factor 8 = k(S)/k(R) exceeds the value of 10 (up to 14) in the most favorable cases. In a properly tuned reaction both the diastereomeric cycloadducts and the enantiomerically enriched dihydrophosphole derivative can be simultaneously obtained in satisfactory chemical and optical yields.
• Pietrusiewicz, K. Michal, Phosphorus, Sulfur and Silicon and the Related Elements, 1996, vol. 109, # 1-4, p. 573 - 576
  作者：Pietrusiewicz, K. Michal

  DOI：——

  日期：——
• Dynamic Kinetic Resolution in Rhodium-Catalyzed Asymmetric Arylation of Phospholene Oxides
  作者：Kelvin Meng-Hui Lim、Tamio Hayashi

  DOI：10.1021/jacs.7b04570

  日期：2017.6.21

  The reaction of 2,5-dihydro-1H-phosphole 1-oxide 1 with ArB(pin) 3 in the presence of a chiral (R)-segphos–rhodium catalyst under highly basic conditions (10 equiv of KOH) gave high yields of (1S,3S)-3-arylphospholane 1-oxide 4 with high diastereoselectivity as well as high enantioselectivity. Equilibration of 1 with its 2,3-dihydro isomer 2, which is chiral and racemic, by base-catalyzed olefin isomerization

  在高碱性条件（10当量的KOH）下，在手性（R）-segphos-铑催化剂的存在下，2,5-二氢-1 H-磷化氢1-氧化物1与ArB（pin）3的反应产生了高收率高非对映选择性和高对映选择性的（1 S，3 S）-3-芳基膦烷1-氧化物4的合成。通过碱催化的烯烃异构化使1与2,3-二氢异构体2（手性和外消旋）平衡，然后用手性铑催化剂进行2的动力学拆分，实现了目前的动态动力学拆分。
• Asymmetric and Doubly Asymmetric 1,3-Dipolar Cycloadditons in the Synthesis of Enantiopure Organophosphorus Compounds
  作者：K. Michaz Pietrusiewicz、Wieszawa Hozody、Marek Koprowski、Stefano Cicchi、Andrea Goti、Alberto Brandi

  DOI：10.1080/10426509908546263

  日期：1999.1.1