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Chiral Bis(dihydrooxazolyl) pyridineruthenium Complexes of trans-Cyclooctene and trans-Cycloheptene

机译:反式-环辛烯和反式-环庚烯的手性双(二氢恶唑基)吡啶钌配合物

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摘要

Asymmetric reaction of an excess of trans-cyclooctene (1) with chiral bis (dihydrooxazolyl) pyridineruthenium (pybox-ip, 3) complex selectively gives the corresponding ruthenium complex 4R, [RuCl_2 (pybox-ip) {(R)-trans-cyclooctene}], and (S)-trans-cyclooctene 2S. The X-ray crystal structure of complex 4R shows a C25-C18-C19-C20 dihedral angle of 125 deg with a C18-C19 bond length of 1.41 A. Complex 4R can also be obtained by UV irradiation of a solution of cis-cyclooctene and [RuCl_2 (pybox-ip) (C_2H_4)] (8) in THF in the presence of a photosensitizer. Even in the absence of the photosensitizer, 4R is produced by irradiation in the presence of cis-cyclooctene. The photoreaction has been applied to cis-cycloheptene to give a 1:1 mixture of the diastereomeric complexes of [Ru(pybox-ip)-{trans-cyclooctene}].
机译:过量的反式环辛烯(1)与手性双(二氢恶唑基)吡啶钌(pybox-ip,3)配合物的不对称反应选择性地得到相应的钌配合物4R,[RuCl_2(pybox-ip){(R)-反式-环辛烯}]和(S)-反式-环辛烯2S。配合物4R的X射线晶体结构显示C25-C18-C19-C20二面角为125度,C18-C19键长为1.41A。配合物4R也可以通过紫外线照射顺式环辛烯溶液获得和[RuCl_2(pybox-ip)(C_2H_4)](8)在THF中在光敏剂的存在下。即使在不存在光敏剂的情况下,通过在顺式环辛烯的存在下照射也可以产生4R。已将光反应应用于顺式环庚烯,以得到[Ru(pybox-ip)-{trans-cyclooctene}]的非对映体复合物的1:1混合物。

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