【摘要】：本論文主要研究手性氮膦配體、2,3-二取代-5-乙烯基-4,5-二氫呋喃衍生物以及2-次甲基吡咯環(huán)衍生物的合成。1.合成了一系列酰胺類及亞胺類手性氮膦配體。首先,將生物堿辛可寧衍生為伯胺化合物,然后與2-(二苯基氧膦)苯甲酸通過脫水縮合合成最簡單的酰胺類手性氮膦配體,緊接著通過插入不同氨基酸合成了一系列酰胺鍵類手性配體。同時,將辛可寧伯胺化合物與不同氨基酸及2-(二苯基膦)苯甲醛通過脫水縮合反應(yīng)合成不同系列的亞胺類手性氮膦配體。2.在金屬催化劑與配體協(xié)同催化下,利用烯丙基二碳酸酯與β-酮酯通過分子間的C-烯丙基化反應(yīng)與分子內(nèi)的O-烯丙基化反應(yīng)合成2,3-二取代-5-乙烯基-4,5-二氫呋喃衍生物。通過對實驗反應(yīng)參數(shù)進行優(yōu)化,最終選擇以2 mol%Pd(PPh3)4與2 mol%1,2-雙(二苯基膦)乙烷作為高效催化體系,并在此高效催化體系下合成一系列2,3-二取代-5-乙烯基-4,5-二氫呋喃衍生物。結(jié)果表明,反應(yīng)底物含有吸電子基團時反應(yīng)具有較高的反應(yīng)活性及產(chǎn)率。隨后,又利用所合成的手性氮膦配體與金屬協(xié)同作用合成手性2,3-二取代-5-乙烯基-4,5-二氫呋喃衍生物,雖然沒有得到較高ee值的手性目標產(chǎn)物,但為后續(xù)的研究提供了實驗經(jīng)驗和理論指導。3.在合成的手性氮膦配體、金屬以及堿的共同催化下,以末端炔基二碳酸酯與保護的亞胺為底物,通過Mannich反應(yīng)及炔氫胺化串聯(lián)環(huán)化反應(yīng)合成2-次甲基吡咯環(huán)衍生物,并對反應(yīng)條件-金屬催化劑、手性配體及反應(yīng)溶劑進行篩選優(yōu)化,在優(yōu)化的條件下成功得到目標產(chǎn)物,其產(chǎn)率為83%,ee值為65%。
[Abstract]:This paper mainly deals with the synthesis of chiral nitrogen-derived ligands, 2,3-disubstituted-5-vinyl-4,5-dihydro-derivatives and 2-methomorphin derivatives. A series of chiral amine and imine chiral nitrogen-derived ligands were synthesized. First, the alkaloid cinchonine is derived as a primary amine compound, and then is synthesized by dehydration condensation with 2-(diphenyl oxide) benzoic acid to synthesize the simplest triamine-like chiral nitrogen-derived ligand, followed by the synthesis of a series of amine-like chiral ligands by inserting different amino acids. In that same time, the compound of the primary amine of the cinchonine and the different amino acid and 2-(diphenylmethyl) benzaldehyde are synthesized by a dehydration condensation reaction to synthesize a different series of imine chiral nitrogen-based ligands. 2,3-disubstituted-5-vinyl-4,5-dihydro-derivatives are synthesized by the C-allylation reaction between the molecules and the O-allylation reaction in the molecule with the co-catalysis of the metal catalyst and the ligand. The experimental reaction parameters were optimized,2 mol% Pd (PPh3)4 and 2 mol% 1,2-bis (diphenylmethyl) ethane were selected as the high efficiency catalytic system, and a series of 2,3-disubstituted-5-vinyl-4,5-dihydro-derivatives were synthesized in this efficient catalytic system. The results show that the reaction substrate has higher reaction activity and yield when the electron-withdrawing group is contained in the reaction substrate. Subsequently, the chiral 2,3-disubstituted-5-vinyl-4,5-dihydro-derivatives of the chiral 2,3-disubstituted-5-vinyl-4,5-dihydro-derivatives was synthesized by the combination of the synthesized chiral nitrogen-base ligand and the metal, although the chiral target product of the higher ee value was not obtained, the experimental experience and the theoretical guidance were provided for subsequent studies. under the co-catalysis of the synthesized chiral nitrogen-base ligand, the metal and the base, the terminal alkynyl dicarbonate and the protected imine are used as a substrate, and the 2-methomorphin ring derivative is synthesized through the Mannich reaction and the hydroamination series cyclization reaction, and the reaction condition-metal catalyst is prepared, The chiral ligand and the reaction solvent are screened and optimized, and the target product is successfully obtained under the optimized conditions, and the yield is 83% and the ee value is 65%.
【學位授予單位】：湖南工業(yè)大學
【學位級別】：碩士
【學位授予年份】：2015
【分類號】：R914.5

【參考文獻】

相關(guān)期刊論文 前1條

1 ;New Chiral Metal Cluster Systems for Catalytic AsymmetricSyntheses of Chiral Alcohols[J];Chemical Research in Chinese Universities;2004年02期

，

本文編號：2501451