Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/90566
標題: Palladium-catalyzed Suzuki-Miyaura and Catellani Reactions Employing Five-membered Heterocycle Substituted Phosphinous Acid Ligands
製備五圓雜環取代之亞膦酸配位基應用於鈀金屬催化Suzuki-Miyaura與Catellani反應
作者: 毛國仲
Kuo-Chung Mao
關鍵字: Suzuki-Miyaura reaction;Catellani reaction;SPO;catalytic reaction;亞膦酸;二級氧化膦基;催化反應
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摘要: 
Several new phosphinous acids (3s) having five-membered heterocycle skeleton were prepared. These new compounds can be tautomerized to each corresponding secondary phosphine oxides (SPOs) which are air-stable and efficient pre-ligands for some transition metal catalytic reactions.
A platinum phohphine complex (5b_trans) was obtained from the reaction of PtCl2 with ligand (3b). The structure of 5b_trans reveals that the platinum metal center of the square planar geometry is coordinated by two 3b ligands in a trans and mono-dentate manner. It is believed that the palladium counterpart shall have similar bonding mode although its crystal structure is not available.
Applications of these SPO ligands (3a-3d) in Suzuki-Miyaura cross-coupling reactions exhibited fair to excellent efficiencies. Preliminary results also show that these ligands also act as effective ligands for palladium catalyzed Carellani reaction.

本研究製備數種新型的五圓雜環取代之亞膦酸(Phosphinous Acid, PA)配位基(3s),亞膦酸配位基(3s)在溶液中可經由互變異構化轉為結構上較為穩定的二級氧化膦基(Secondary phosphine oxide, SPO)。
  由配位基(3s)與金屬反應可形成錯合物。其中,由配位基(3b)與PtCl2反應得到反式鉑金屬錯合物晶體結構(5b_trans),此錯合物(5b_trans)對空氣及水氣很穩定,可以保存許久。同時印證配位基(3b)具有單牙基型式的配位能力。
  將這一系列的二級氧化膦基配位基(3s)與鈀金屬結合作為催化劑,應用於Suzuki-Miyaura 耦合,可得到還不錯的效率。另外,本研究也將配位基(3b)與鈀金屬結合應用於催化Catellani反應,此為多成分骨牌反應(Domino reaction),在初步測試可以發現有一定的催化能力。
URI: http://hdl.handle.net/11455/90566
Rights: 同意授權瀏覽/列印電子全文服務,2014-07-17起公開。
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