(R)-Ir-SEGPHOS | 1346158-92-6

• 英文名称: (R)-Ir-SEGPHOS
• CAS: 1346158-92-6；1346158-93-7
• 化学式: C₅₅H₃₉IrN₂O₄P₂
• 分子量: 1046.09
• InChiKey: GNQMDGUYEVBYBM-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  乙酸烯丙酯 、 4-氰基-3-硝基苯甲酸 、 bis(1,5-cyclooctadiene)diiridium(I) dichloride 、 (R)-2,2'-bis(diphenylphosphanyl)-1,1'-binaphthyl 在 caesium carbonate 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以63%的产率得到(R)-Ir-SEGPHOS
  参考文献：
  名称：

  Redox-Triggered C–C Coupling of Alcohols and Vinyl Epoxides: Diastereo- and Enantioselective Formation of All-Carbon Quaternary Centers via tert-(Hydroxy)-Prenylation

  摘要：

  Iridium catalyzed primary alcohol oxidation triggers reductive C-O bond cleavage of isoprene oxide to form aldehyde-allyliridium pairs that combine to form products of tert-(hydroxy)-prenylation, a motif found in >2000 terpenoid natural products. Curtin-Hammett effects are exploited to enforce high levels of anti-diastereo- and enantioselectivity in the formation of an all-carbon quaternary center. The present redox-triggered carbonyl additions occur in the absence of stoichiometric byproducts, premetalated reagents, and discrete alcohol-to-aldehyde redox manipulations.

  DOI：

  10.1021/ja504625m
• 作为试剂：
  描述：

  2-乙烯基环丙烷-1,1-二羧酸二甲酯 、 1-壬醇 在 potassium phosphate 、 (R)-Ir-SEGPHOS 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 48.0h， 生成 dimethyl 2-((2S,3R)-3-hydroxy-2-vinylundecyl)malonate 、 dimethyl 2-(3-hydroxy-2-vinylundecyl)malonate
  参考文献：
  名称：

  Polarity Inversion of Donor–Acceptor Cyclopropanes: Disubstituted δ-Lactones via Enantioselective Iridium Catalysis

  摘要：

  The coupling of carbonyl electrophiles at the donor position of donor acceptor cyclopropanes is described, representing an inversion of polarity with respect to conventional reactivity modes displayed by these reagents. Specifically, upon exposure of donor-acceptor cyclopropanes to alcohols in the presence of a cyclometalated iridium catalyst modified by (S)-BINAP, catalytic C-C coupling occurs, providing enantiomerically enriched products of carbonyl allylation. Identical products are obtained upon isopropanol-mediated transfer hydrogenation of donor acceptor cyclopropanes in the presence of aldehydes. The reaction products are directly transformed to cis-4, 5-disubstituted delta-lactones.

  DOI：

  10.1021/ja2090993

文献信息

• Enantioselective Iridium-Catalyzed Allylic Alkylation of Racemic Branched Alkyl-Substituted Allylic Acetates with Malonates
  作者：Tian-Yuan Zhang、Yi Deng、Kun Wei、Yu-Rong Yang

  DOI：10.1021/acs.orglett.0c04309

  日期：2021.2.5

  The regio- and enantioselective allylic substitution of branched alkyl-substituted allylic acetates employing malonates has been achieved through a process that calls for Krische’s π-allyliridium C,O-benzoate catalyst. The protocol reported herein can be applied to a diverse set of branched alkyl substrates that are generally not well tolerated in the other two types of Ir-catalyzed allylation.

  使用丙二酸酯的支链烷基取代的烯丙基乙酸酯的区域和对映选择性烯丙基取代是通过要求Krische的π-烯丙基铱C，O-苯甲酸酯催化剂的方法实现的。本文报道的方案可应用于通常在其他两种类型的Ir催化的烯丙基化中不能很好耐受的各种支链烷基底物上。