ISODICYCLOPENTADIENES AND RELATED MOLECULES .38. HOMOCHIRAL PINENE-FUSED CYCLOPENTADIENES - SYNTHESIS AND PI-FACIALLY SELECTIVE COURSE OF DIELS-ALDER CYCLOADDITIONS AND METALLOCENE FORMATION
ISODICYCLOPENTADIENES AND RELATED MOLECULES .38. HOMOCHIRAL PINENE-FUSED CYCLOPENTADIENES - SYNTHESIS AND PI-FACIALLY SELECTIVE COURSE OF DIELS-ALDER CYCLOADDITIONS AND METALLOCENE FORMATION
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DOI：
10.1021/jo00230a015
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发表时间：
1987-10-16
影响因子：
3.6
通讯作者：
MCLAUGHLIN, ML
中科院分区：
文献类型：
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作者：
PAQUETTE, LA;GUGELCHUK, M;MCLAUGHLIN, ML
同手性(LFI)-(-)-9，9-二甲基三环[6.1.合成了1，02，6]十-2，5-二烯(3)，并研究了其与N-苯基马来酰亚胺、对苯二酚、乙酰二甲酸二甲酯和(Z)-L的Diels-Alder反应。正如预期的那样，[4+2]环加成反应最好从受阻较小的表面发生，尽管程度不同。3或3的阴离子分别与Fe(CO)5和TiCl4反应，在每种情况下只提供单一的茂金属，络合发生在从SYN方向到甲基桥的位置。4-二甲氨基取代的富烯4与六氟磷酸盐29和35发生配体转移反应，形成异构体对。平面上的协调再次被证明占主导地位。因此，与异双环戊二烯(1)和异双环戊三烯(2)形成鲜明对比的是，3和4始终主要或完全通过单面结合。异双环戊二烯(I)及其脱氢衍生物2几年前被认为是平面非对称双烯，为研究表面选择性提供了相当大的空间。3-5 Diels-Alder，6，7[6+4]，8和[3+4]环的显著立体化学结果-
Homochiral (lfi)-(-)-9, 9-dimethyltricyclo [6.1. 1.02, 6] deca-2, 5-diene (3) has been synthesized and its Diels-Alder reactions with N-phenylmaleimide, p-benzoquinone, dimethyl acetylenedicarboxylate, and (Z)-l, 2-bis (phenyl-sulfonyl) ethylene investigated. As expected,[4+ 2] cycloaddition occurs preferably from the less-hindered-surface, although to varying degrees. Reaction of 3 or the anion of 3 with Fe (CO) 5 and TiCl4, respectively, is shown to provide only a single metallocene in each instance, complexation occurring from the direction syn to the methano bridge. The ligand transfer reactions of the 4-(dimethylamino)-substituted fulvene 4 with thehexafluorophosphates 29 and 35 gave rise to isomeric pairs of complexes. Above-plane coordination was again shown to predominate. Thus, 3 and 4 consistently undergo binding predominantly or exclusively from one-face, in striking contrast to the behavior of isodicyclopentadiene (1) and isodicyclopentatriene (2).Isodicyclopentadiene (I) and its dehydro derivative 2 were recognized several years ago to be plane-nonsymmetric dienes offering considerable latitude for the study of-facial selectivity. 3-5 The remarkable stereochemical outcome of Diels-Alder, 6, 7 [6+ 4], 8 and [3+ 4] cyclo-