Absolute stereochemistry assignment of N-phosphorylimine-derived aza-Diels-Alder adducts with TDDFF CD calculations
Absolute stereochemistry assignment of N-phosphorylimine-derived aza-Diels-Alder adducts with TDDFF CD calculations
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DOI：
10.1002/chir.20167
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发表时间：
2005-06-01
期刊：
影响因子：
2
通讯作者：
Whiting, A
中科院分区：
文献类型：
--
作者：
Di Bari, L;Guillarme, S;Whiting, A
N-磷酰亚胺与Danishefsky二烯发生刘易斯酸催化的Diels-Alder反应。手性催化剂锌（II）-（S）-BINOL的应用导致良好至低的不对称诱导，但化学转化率差。然而，新的氮杂-狄尔斯-桤木环加合物，如二乙基4-氧代-2-苯基-3，4-二氢吡啶-1（2 H）-基膦酸酯的绝对立体化学，可以使用圆二色性（CD）测定。实验和TDDFT计算的CD谱之间的比较表明，使用（S）-催化剂的结果在（6 R）环加合物的主要形成。(c)2005 Wiley-Liss，Inc.
N-Phosphorylimines undergo Lewis acid-catalyzed Diels-Alder reactions with Danishefsky's diene. Application of the chiral catalyst zinc (II)- (S)-BINOL results in good-to-low asymmetric induction but poor chemical conversion. However, the absolute stereochemistry of novel aza-Diels-Alder cycloadducts, such as diethyl 4-oxo-2-phenyl-3,4-dihydropyridin-1(2H)-ylphosphonate, can be determined using circular dichroism (CD). Comparison between experimental and TDDFT-calculated CD spectrum shows that use of the (S)-catalyst results in predominant formation of the (6R) cycloadducts. (c) 2005 Wiley-Liss, Inc.