过渡金属催化的酮羰基导向C—H键官能化反应进展

doi:10.6023/cjoc202205033

摘要/Abstract

近二十年来, 过渡金属催化的酮羰基导向C—H键活化已发展成为在酮的非传统反应位点构建碳碳键和碳杂键(杂原子为氮、氟和氧原子等)的强有力而快捷的手段. 其中, 钌、铑、钯、铱等贵金属催化的酮羰基导向C—H键活化反应得到了广泛研究, 而廉价3d金属锰、铁和钴催化的酮羰基导向C—H活化反应逐渐成为当前研究的热点. 文中按照过渡金属催化的酮羰基导向C—H键官能化的不同反应类型(烷基化、烯基化、酰胺化、芳基化、环化等)综述了该领域近年来(2014~2021)的研究进展.

关键词: 过渡金属, 催化, 酮羰基, C—H键官能化, 有机合成

In the past two decades, transition-metal-catalyzed keto carbonyl-directed C—H bond activation has evloved as a powerful and convenient tool for the construction of C—C and C—X (X=N, F, O) bonds at the unconventional reaction sites of ketones. Among them, keto carbonyl-directed C—H bond activation reactions catalyzed by noble metals, involving ruthenium, rhodium, palladium and iridium, have been widely explored, whilst inexpensive 3d metals, such as manganese, iron and cobalt, have gradually emerged as hotspot catalysts in keto carbonyl-directed C—H activation reactions recently. In this review, advances on transition-metal-catalyzed keto carbonyl-directed C—H bond functionalization reactions from 2014 to 2021 are summarized, which are devided by reaction categories such as alkylation, alkenylation, amidation, arylation, cyclization, and so on.

Key words: transition metals, catalysis, keto carbonyl, C—H bond functionalization, organic synthesis

引用此文

陈泗林, 杨芸辉, 陈超, 王从洋. 过渡金属催化的酮羰基导向C—H键官能化反应进展[J]. 有机化学, 2023, 43(1): 1-16.

Silin Chen, Yunhui Yang, Chao Chen, Congyang Wang. Advances in Transition-Metal-Catalyzed Keto Carbonyl-Directed C—H Bond Functionalization Reactions[J]. Chinese Journal of Organic Chemistry, 2023, 43(1): 1-16.

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图/表 29

图式1. 铱催化芳酮邻位C—H键支链选择性烷基化反应

Scheme 1. Iridium-catalyzed C—H bond branch-selective alkylation of aryl ketones

图式2. 铁催化芳酮邻位C—H键直链选择性烷基化反应

Scheme 2. Iron-catalyzed C—H bond linear alkylation of aryl ketones

图式3. 钌催化2-/3-芳酰基苯并[b]呋喃与丙烯酸酯的C—H键烷基化反应

Scheme 3. Ruthenium-catalyzed C—H bond alkylation of 2-/3- aroylbenzofurans with acrylates

图式4. 钌/铑催化的芳酮邻位C—H键对马来酰亚胺的加成反应

Scheme 4. Ruthenium/Rhodium-catalyzed addition reactions of ortho C—H bond of aryl ketones to maleimides

图式5. 钯催化的吲哚C(4)—H键与高价碘盐的氟烷基化反应

Scheme 5. Palladium-catalyzed C(4)—H bond fluoroalkylation of indoles with hypervalent iodonium salts

图式6. 铑/铱催化的芳酮C—H键与重氮酯的烷基化反应

Scheme 6. Rhodium/Iridium-catalyzed C—H bond alkylation of (hetero)aromatic ketones with diazo esters

图式7. 铁催化的芳香化合物的邻位甲基化反应

Scheme 7. Iron-catalyzed ortho methylation of aromatic compounds

图式8. 钴催化的芳香化合物的邻位烷基化反应

Scheme 8. Cobalt-catalyzed ortho alkylation of aromatic compounds

图式9. 钯催化的远端C(sp2)—H键烯基化反应

Scheme 9. Palladium-catalyzed alkenylation of distal C(sp2)—H bond

图式10. 锰催化的芳香酮的邻位烯基化反应

Scheme 10. Manganese-catalyzed ortho-olefination of aromatic ketones

图式11. 铑/钌/钴催化的氧化型Heck偶联反应

Scheme 11. Rhodium/Ruthenium/Cobalt-catalyzed oxidative Heck-type coupling reactions

图式12. 钌催化的芳香酮与烯丙基砜的邻位烯基化反应

Scheme 12. Ruthenium-catalyzed ortho olefination of aromatic ketones with allyl sulfones

图式13. 钌催化的芳香酮与炔烃的邻位烯基化反应

Scheme 13. Ruthenium-catalyzed ortho olefination of aromatic ketones with alkynes

图式14. 酮羰基导向的芳烃C(sp2)—H键的酰胺化反应

Scheme 14. Keto carbonyl-directed C(sp2)—H amidation of arenes

图式15. 酮羰基导向的吲哚衍生物的C(sp2)—H键的酰胺化反应

Scheme 15. Keto carbonyl-directed C(sp2)—H amidation of indole derivatives

图式16. 烯胺酮羰基导向的芳烃C(sp2)—H键的酰胺化反应

Scheme 16. Enaminone-directed C(sp2)—H amidation of arenes

图式17. 酮羰基导向的芳烃与硼酸酯的C—H键的芳基化反应

Scheme 17. Keto carbonyl-directed C—H arylation of arenes with arylboronates

图式18. 钯催化的芳酮C—H键的脱氢偶联反应

Scheme 18. Palladium-catalyzed C—H dehydrogenative cross coupling reaction of aromatic ketones

图式19. 钌催化的原位芳酮C—H键的芳基化反应

Scheme 19. Ruthenium-catalyzed C—H arylation of aromatic ketones formed in situ

图式20. 酮羰基导向的杂芳烃C—H键的芳基化反应

Scheme 20. Keto carbonyl-directed C—H arylation of heteroarenes

图式21. 酮羰基导向的分子内C—H键活化并环化反应

Scheme 21. Keto carbonyl-directed intramolecular annulation via C—H activation

图式22. 内炔参与的C—H键活化并环化反应

Scheme 22. Sequential C—H activation and annulation involving internal alkynes

图式23. 锰催化的C—H键活化并环化反应

Scheme 23. Sequential C—H activation and annulation catalyzed by manganese

图式24. 钴催化C—H键活化合成茚

Scheme 24. Synthesis of indene derivatives via Cobalt-cata- lyzed C—H activation

图式25. 铑催化C—H键活化合成咔唑酮类化合物

Scheme 25. Synthesis of carbazolone derivatives via Rhodium-catalyzed C—H activation

图式26. 酮羰基导向的C—H键烯丙基化反应

Scheme 26. Keto carbonyl-directed C—H allylation

图式27. 酮羰基导向的C—H键酰基化反应

Scheme 27. Keto carbonyl-directed C—H acylation

图式28. 酮羰基导向的C—H键氟化反应

Scheme 28. Keto carbonyl-directed C—H fluorination

图式29. 酮羰基导向的C—H键氧化反应

Scheme 29. Keto carbonyl-directed C—H oxygenation

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