三苯基磷催化α-位取代丙二烯酯和缺电子烯的［4+2］环化反应研究
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摘要
本论文包括以下三部分：
(1)总结了近年来磷化物和胺等Lewis碱催化的丙二烯酯参与的和醛,缺电子烯,亚胺的反应,着重的介绍了有机磷化物催化的丙二烯酯和醛,缺电子烯,亚胺的环化反应过程。
(2)三苯基磷催化α-位取代丙二烯酯和缺电子烯的[4+2]环化反应研究。使用PPh3催化,发展了通过α-酯基取代丙二烯酯和缺电子苄烯丙二腈的环化反应合成多取代环己烯衍生物的新途径,经X-射线单晶衍射确证了产物的结构。对底物的适用范围进行了拓展,发现邻位取代苯基具有较好的区域选择性。
(3)研究了末端炔烃对手性α-氨基叔丁基亚磺酰亚胺的不对称加成反应。以天然氨基酸为起始原料,经邻苯二甲酰基保护氨基,再与(S)-叔丁基亚磺酰胺合成亚胺。利用炔基锌对其进行不对称加成,以较高非对映选择性(95：5->99：1)得到了手性炔基二胺衍生物。将邻苯二甲酰基和叔丁基亚磺酰基依次脱除,发展了一种合成手性炔基二胺的新方法。
This thesis is composed of three parts:
(1) Nucleophilic phosphine and amine catalysis has proven to be a powerful tool in organic synthesis. Investigations in this area have established a range of suitable coupling partners for allenoates, including electron-deficient olefins, imines, and aldehydes. Especially, Nucleophilic phosphine catalysis which can provide easy access to cyclic, bicyclic or polycyclic carbocycles and heterocycles. This chapter will summary the recent achievements in this area.
(2) We have developed a [4+2] annulations of a-alkylallenoates with arylidenemalononitriles catalyzed by triphenylphosphine. The highly functionalized cyclohexene derivatives were afforded in moderate yields (60-78%).
(3) We have developed the asymmetric addition reactions of nucleophilic acetylides to a-amino N-tert-butanesulfinimines, which were synthesized from L-amino acids. The desired a-(phthaloyl-imide) propargyl amines were obtained in good distereoselectivities (95:5 to>99:1 dr) under optimized conditions. The propargyl diamine was obtained by deprotecting of the phthalimide and N-tert-butanesulfinyl groups.
(1)总结了近年来磷化物和胺等Lewis碱催化的丙二烯酯参与的和醛,缺电子烯,亚胺的反应,着重的介绍了有机磷化物催化的丙二烯酯和醛,缺电子烯,亚胺的环化反应过程。
(2)三苯基磷催化α-位取代丙二烯酯和缺电子烯的[4+2]环化反应研究。使用PPh3催化,发展了通过α-酯基取代丙二烯酯和缺电子苄烯丙二腈的环化反应合成多取代环己烯衍生物的新途径,经X-射线单晶衍射确证了产物的结构。对底物的适用范围进行了拓展,发现邻位取代苯基具有较好的区域选择性。
(3)研究了末端炔烃对手性α-氨基叔丁基亚磺酰亚胺的不对称加成反应。以天然氨基酸为起始原料,经邻苯二甲酰基保护氨基,再与(S)-叔丁基亚磺酰胺合成亚胺。利用炔基锌对其进行不对称加成,以较高非对映选择性(95：5->99：1)得到了手性炔基二胺衍生物。将邻苯二甲酰基和叔丁基亚磺酰基依次脱除,发展了一种合成手性炔基二胺的新方法。
This thesis is composed of three parts:
(1) Nucleophilic phosphine and amine catalysis has proven to be a powerful tool in organic synthesis. Investigations in this area have established a range of suitable coupling partners for allenoates, including electron-deficient olefins, imines, and aldehydes. Especially, Nucleophilic phosphine catalysis which can provide easy access to cyclic, bicyclic or polycyclic carbocycles and heterocycles. This chapter will summary the recent achievements in this area.
(2) We have developed a [4+2] annulations of a-alkylallenoates with arylidenemalononitriles catalyzed by triphenylphosphine. The highly functionalized cyclohexene derivatives were afforded in moderate yields (60-78%).
(3) We have developed the asymmetric addition reactions of nucleophilic acetylides to a-amino N-tert-butanesulfinimines, which were synthesized from L-amino acids. The desired a-(phthaloyl-imide) propargyl amines were obtained in good distereoselectivities (95:5 to>99:1 dr) under optimized conditions. The propargyl diamine was obtained by deprotecting of the phthalimide and N-tert-butanesulfinyl groups.
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