Bicyclo [3, 1, 0] Hexane For The Skeleton Type Of Photochemical Reaction Of Norrish Ⅱ

NorrishⅡtype of photochemical reaction withγ-H refers to carbonyl compounds in the light occursγ- H migration to produce 1, 5 - double radical compounds, followed by C- C bond cleavage to form olefins and ketones. The reaction is a good halo reaction in organic synthesis, especially in the total synthesis of natural products with a wide range of applications. The main content of this paper is to study the bicyclo [3, 1, 0] hexane compounds as the backbone of the photochemical reaction of NorrishⅡtype to PGE1 synthesis of natural products important intermediate compounds for the total synthesis of PG series compounds. It lies a good foundation for the five-membered ring of the building blocks provides a new way of thinking.Chapter 1: It reviews the recent application of chiral reagents, the photochemical reaction of principle, application, synthesis of cyclopentene derivatives and total synthesis of prostaglandins. Focused on the development of organic photochemistry summarizes the characteristics of the main types, the synthesis of cyclopentene derivatives and its application of prostaglandin synthetic drugs.Chapter 2: Design of the Ring [3, 1, 0] hexane as a skeleton, with the photochemical reaction of NorrishⅡtype precursors and photochemical characteristics of a reasonable response to the two routes, and were tried on the two routes. Eventually nbd as raw materials, excess acid rearrangement, reduction, protection of silicon ether, sodium borohydride oxidation, protection and selective deprotection, oxidation, format reagent addition, oxidation, deprotection, etc. are 10 steps to success photochemical precursor of the target, the total yield was 4.94 %; experiment for each step of the experimental conditions were optimized, and strive to find the best conditions in order to obtain a higher yield, and put forward some reasonable improvement steps programs laid the conditions for the follow-up; of the target product was synthesized HPLC, gas chromatography -mass spectrometry, liquid chromatography - mass spectrometry, nuclear magnetic resonance spectroscopy, carbon nuclear magnetic resonance spectroscopy, 1H - 1HCOSY, DEPT 135, HMQC, HMBC , ROESY, NOE and other spectrum tests show that the compound was successfully synthesized and characterized by nuclear magnetic resonance with two-dimensional photochemical precursors are given two-dimensional spatial structure of 10. Chapter 3: The synthesized target compounds were a series of light reaction test results show that the precursors of photochemical photochemical reaction of 10 occurred. Optimized during testing in order to achieve higher light yield. According to HPLC and NMR spectral analysis results show that the photochemical reaction of the desired product, combined with the photochemical reaction of NorrishⅡtype response characteristics inferred that the reaction mechanism of the photochemical reaction. According to experimental results light test steps proposed improvement scheme for the syntheses of the light response and follow-up to lay the foundation for the total synthesis of PGE series of compounds provides a new way of thinking, but also for the photochemical reaction in natural products total synthesis application provides a good example.Chapter 4: Synthesis of listed and part of the experiment in the spectra of compounds for further synthesis and light reactions provide a reference.