基于α-叔碳-β,γ-不饱和醛的制备全合成番茄红素

Synthesis of Lycopene Based on Preparation of β,γ-Unsaturated Aldehyde with α-Tertiary Center

摘要:

将一种α-取代-α,β-不饱和醛的制备方法应用于番茄红素(Ⅵ)的全合成中，通过该方法以廉价的原料假性紫罗兰酮(Ⅰ)制备了2, 6, 10-三甲基-3, 5, 9-十一烷三烯-1-醛(Ⅱ)，然后与四乙基亚甲基二磷酸酯(Ⅲ)经过Wittig-Horner反应得到关键中间体3, 7, 11-三甲基-1, 4, 6, 10-四烯十二烷基膦酸二乙酯(Ⅳ)，最终和2, 7-二甲基-2, 4, 6-辛三烯-1, 8-二醛(Ⅴ)进行Wittig-Horner反应、转位异构合成全反式番茄红素。反应共经历3步线性反应，总产率为37.0%。最终产物的结构采用IR、HRMS和NMR进行确证。

Abstract:

Lycopene(Ⅵ) was synthesized via α,β-unsaturated aldehyde with α-tertiary center strategy. Firstly, Pseudoionone(Ⅰ), an inexpensive raw material, was adopted to synthesize 2, 6, 10-trimethylundeca-3, 5, 9-trienal (Ⅱ). Then the key intermediate, diethyl (3, 7, 11-trimethyldodeca-1, 4, 6, 10-tetraenyl) phosphonate(Ⅳ), was formed by Wittig-Horne reaction of the aldehyde II and tetraethyl methylenebis-phosphonate(Ⅲ). The final product, all-E lycopene, can be collected after Wittig-Horner reaction and isomers rearrangement of compound Ⅳ and 2, 7-dimethylocta-2, 4, 6-triene-1, 8-dial(Ⅴ). The synthesis of lycopene needed only 3 steps, with the yield of 37.0%. The structure of all-E lycopene was characterized by IR, HRMS and NMR techniques.