有機合成化学協会誌
Online ISSN : 1883-6526
Print ISSN : 0037-9980
ISSN-L : 0037-9980
Pincer型ビスオキサゾリニルフェニル (Phebox) を不斉配位子とする光学活性遷移金属ルイス酸錯体の合成と不斉反応への応用
本山 幸弘西山 久雄
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ジャーナル フリー

2003 年 61 巻 4 号 p. 343-351

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Optically active bis (oxazolinyl) phenyl (Phebox) was designed as an anionic N-C-N pincer ligand, and (Phebox) SnMe3 was prepared as its stable precursor. The aqua complexes, (Phebox) RhIIIX2H2O) [X=Cl, Br, F], [(Phebox) MII (H2O)] (BF4) [M=Pd, Pt] and [(Phebox) PtIV (H2O)] (BF4), were synthesized by the oxidative addition or transmetallation of RhI, PdII and PtII precursors with (Phebox) SnMe3 and subsequent ligand exchange reaction. X-ray structure studies revealed that the octahedral structure of RhIII complex is isosteric with the PtIV, and the PdII and PtII complexes are almost the same configuration with a square-planar structure. These aqua complexes acted as efficient catalysts for enantioselective allylation of aldehydes with allyltin reagents, hetero Diels-Alder reaction of Danishefsky's diene with glyoxylates and the aldol-type condensation of tosylmethyl isocyanide with aldehydes. While (Phebox) RhIII (SnMe3) Cl complexes catalyzed the Michael addition of α-cyanopropionates to acrolein.

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