碳氢链的选择性多位点官能化反应研究进展

doi:10.6023/cjoc202404010

摘要/Abstract

碳氢链的选择性官能化是合成化学中的重要科学问题, 从简单易得的烷烃或烯烃出发直接官能化是其高效和高附加值转化的理想方法, 其中碳氢链上[包括C=C双键和C(sp³)—H键]选择性多位点官能化可以通过一步反应同时构建多个化学键, 从而极大地提高化合物的合成效率. 例如碳氢链多乙酰氧化反应可以用于多羟基糖类化合物的高效制备, 尤其是在生物和医药领域有重要价值但在自然界中罕见的稀有单糖. 从烷烃的多位点官能化和烯烃的多位点官能化反应两个方面总结了近年来碳氢链选择性多位点官能化反应的研究进展.

关键词: 碳氢链, 选择性, 多位点, 官能化

Selective functionalization of hydrocarbon chains is an important scientific problem in synthetic chemistry, and direct functionalization of easily available alkanes or alkenes is an ideal method for their efficient and high value-added conversion. Selective multi-site functionalization on the hydrocarbon chain (including C=C double bonds and C(sp³)—H bonds) can construct multiple chemical bonds in a one-step reaction, greatly improving the synthesis efficiency of compounds. For example, the multi-acetoxylation of hydrocarbon chains can be used for the efficient preparation of polyhydroxyl compounds, especially rare monosaccharides that are of great value in biology and medicine but rarely found in nature. The research progress in selective multi-site functionalization of hydrocarbon chains in recent years summarized from two aspects: multi-site functionalization of alkanes and multi-site functionalization of alkenes.

Key words: hydrocarbon chain, selectivity, multi-site, functionalization

引用此文

王军威, 刘慧康, 杨泽华, 吴正兴, 张万斌. 碳氢链的选择性多位点官能化反应研究进展[J]. 有机化学, 2024, 44(11): 3273-3281.

Junwei Wang, Huikang Liu, Zehua Yang, Zhengxing Wu, Wanbin Zhang. Research Progress on Selective Multi-site Functionalization of Hydrocarbon Chains[J]. Chinese Journal of Organic Chemistry, 2024, 44(11): 3273-3281.

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图/表 15

图式1. 碳氢链的选择性官能化反应

Scheme 1. Selective functionalization of hydrocarbon chains

图式2. 烷烃和烯烃的选择性多官能化反应

Scheme 2. Selective multi-functionalization of alkanes and alkenes

图式3. 胺基取代烷烃的多溴化反应

Scheme 3. Multi-bromination of amine-substituted alkanes

图式4. 芳基或酰胺取代的烷烃的多乙酰氧化反应

Scheme 4. Multi-acetoxylation of aryl- or amide-substituted alkanes

图式5. 烷烃的多乙酰氧化反应机理

Scheme 5. Mechanism of multi-acetoxylation of alkanes

图式6. 苯亚硒酸酐和三氟乙酸酐作用下的烯烃的三官能化反应

Scheme 6. Trifunctionalization of alkenes enabled by benzeneseleninic and trifluoroacetic anhydrides

图式7. 钯催化烯烃的脱氢双胺化反应

Scheme 7. Palladium-catalyzed dehydrogenative diamination of alkenes

图式8. 钯催化烯烃的脱氢双胺化反应机理

Scheme 8. Mechanism of palladium-catalyzed dehydrogenative diamination of alkenes

图式9. 腙自由基参与的烯烃三官能化反应

Scheme 9. Trifunctionalization of alkenes involving hydrazone radicals

图式10. 腙自由基参与的烯烃三官能化反应机理

Scheme 10. Mechanism of trifunctionalization of alkenes involving hydrazone radicals

图式11. α,β-不饱和醛的三氧基化反应

Scheme 11. Trioxylation of α,β-unsaturated aldehydes

图式12. 钴催化烯烃的选择性三硼化反应

Scheme 12. Selective triboronation of alkenes catalyzed by cobalt

图式13. 钴催化烯烃的选择性三硼化反应机理

Scheme 13. Mechanism of selective triboronation of alkenes catalyzed by cobalt

图式14. 端烯烃脱氢的1,2-位双和1,2,3-位三乙酰氧化反应

Scheme 14. Dehydrogenative 1,2-diacetoxylation and 1,2,3-triacetoxylation of terminal alkenes

图式15. 端烯烃脱氢的1,2-位双和1,2,3-位三乙酰氧化反应机理

Scheme 15. Mechanism of dehydrogenative 1,2-diacetoxylation and 1,2,3-triacetoxylation of terminal alkenes

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