N-Ts氰胺在有机合成中的研究与应用

doi:10.6023/cjoc202207022

摘要/Abstract

N-Ts氰胺是有机合成中非常高效和实用的一种多功能合成前体, 其在构建含氮骨架领域中获得了较多应用. 根据反应类型划分, 总结了近年来N-Ts氰胺在有机合成中的研究进展, 主要包括其在氰基化反应、经氰胺负离子参与的环化反应、氰胺化反应、磺酰化反应及经氰基官能团参与的环化反应等方面的应用, 并对该领域的研究前景进行了展望.

关键词: N-Ts氰胺, 氰基化, 氰胺化, 磺酰化, 环化反应

N-Ts cyanamide, which has been widely used in the construction of nitrogen-containing framework, is one of the efficient and practical multifunctional synthetic precursors in organic synthesis. The progress in application of N-Ts cyanamide according to the reaction types is summarized, including the application in cyanation, cyclization reaction via cyanamide anion, cyanamidation, sulfonylation and cyclization reaction via cyano-group. The future development direction of this field is also prospected.

Key words: N-Ts cyanamides, cyanation, cyanamidation, sulfonylation, cyclization reactions

引用此文

王川川, 马志伟, 侯学会, 杨龙华, 陈亚静. N-Ts氰胺在有机合成中的研究与应用[J]. 有机化学, 2023, 43(1): 74-93.

Chuanchuan Wang, Zhiwei Ma, Xuehui Hou, Longhua Yang, Yajing Chen. Research and Application of N-Ts Cyanamides in Organic Synthesis[J]. Chinese Journal of Organic Chemistry, 2023, 43(1): 74-93.

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图/表 40

图式1. N-Ts氰胺的结构及反应类型

Scheme 1. Structure and reactions of N-Ts cyanamides

图式2. 铑催化硼酸的氰基化反应

Scheme 2. Rhodium-catalyzed cyanation of boronic acids

图式3. 铑催化的分子内烯烃氰基化反应

Scheme 3. Rhodium-catalyzed intramolecular cyanation of styrenes

图式4. 铑催化芳基酮肟碳氢键的氰基化反应

Scheme 4. Rhodium-catalyzed C—H cyanation of aryl ketone oximes

图式5. 铑催化芳基异羟肟酸酯邻位碳氢键的氰基化反应

Scheme 5. Rhodium-catalyzed C—H cyanation of aryl hydroxamates

图式6. 铑催化吲哚、吡咯C2位的选择性氰基化

Scheme 6. Rhodium-catalyzed C2-selective cyanation of indoles and pyrroles

图式7. 铑催化二氢吲哚C7位的选择性氰基化

Scheme 7. Rhodium catalyzed C7-selective cyanation of indolines

图式8. 铑催化烯烃碳氢键的氰基化反应

Scheme 8. Rhodium-catalyzed C—H cyanation of alkenes

图式9. 1,4-铑迁移启动的烯烃碳氢键的氰基化反应

Scheme 9. C—H cyanation of alkenes mediated by 1,4-rhodium migration

图式10. 钯催化芳基重氮四氟硼酸盐及卤代芳烃的氰基化反应

Scheme 10. Palladium catalyzed cyanation of arenediazonium tetrafluoroborates and aryl halides

图式11. 芳基羧酸的脱羧氰基化反应

Scheme 11. Decarboxylative cyanation of aryl carboxylic acids

图式12. 钯催化芳基硼酸的氰基化反应

Scheme 12. Palladium-catalyzed cyanation of arylboronic acids

图式13. 铜催化的烯基芳烃的硼化氰基化反应

Scheme 13. Copper-catalyzed borylation/cyanation of vinylarenes

图式14. 铜催化的硼化/邻位氰基化/烯丙基转移串联反应

Scheme 14. Copper-catalyzed borylation/ortho-cyanation/allyl- transfer cascade reaction

图式15. 铜催化取代苯乙烯的硼化/邻位氰基化反应

Scheme 15. Copper-catalyzed borylation/ortho-cyanation of substituted styrenes

图式16. 铜催化末端联烯的1,2,3-三官能团化反应

Scheme 16. Copper-catalyzed 1,2,3-trifunctionalization of terminal allenes

图式17. 铜催化1,3-丁二烯的区域选择性硼氰化反应

Scheme 17. Copper-catalyzed regioselective borylcyanation of 1,3-dienes

图式18. 铜催化1,3-丁二烯的区域选择性硼氰化氧化反应

Scheme 18. Copper-catalyzed regioselective borylcyanation oxidation of 1,3-dienes

图式19. 铜催化1,3-丁二烯的区域选择性不对称硼氰化反应

Scheme 19. Copper-catalyzed regioselective and asymmetric borylcyanation of 1,3-butadienes

图式20. 铜/手性氮杂环卡宾催化联烯的不对称硼氰化反应

Scheme 20. Copper/N-heterocyclic carbene-catalyzed asymmetric borylcyanation of allenes

图式21. 钴催化芳烃邻位碳氢键的氰基化反应

Scheme 21. Cobalt-catalyzed ortho-cyanation of arenes

图式22. 钴催化芳基锌试剂与N-Ts氰胺的交叉偶联反应

Scheme 22. Cobalt-catalyzed cross-coupling reaction of arylzincbromides and N-Ts cyanamides

图式23. 钌催化苯甲酰胺邻位碳氢键的氰基化反应

Scheme 23. Ruthenium-catalyzed ortho-cyanation of benzamides

图式24. 钌催化氮杂吲哚导向芳烃邻位碳氢键的氰基化反应

Scheme 24. Ruthenium-catalyzed C—H cyanation of N-aryl-7- azaindoles

图式25. 镍催化烯烃的还原芳化氰基化反应

Scheme 25. Nickel-catalyzed reductive arylcyanation of alkenes

图式26. 锰催化杂芳烃C2位碳氢键的氰基化反应

Scheme 26. Manganese-catalyzed C2-selective cyanation of heteroarenes

图式27. 吡啶导向锰催化芳烃邻位的氰基化

Scheme 27. Manganese-catalyzed pyridine-directed ortho cyanation of arenes

图式28. 格氏试剂的氰基化反应

Scheme 28. Cyanation of Grignard reagent

图式29. 路易斯酸催化吲哚和吡咯的选择性氰基化反应

Scheme 29. Lewis acid catalyzed regioselective cyanation of indoles and pyrroles

图式30. 硼试剂促导酮类化合物的亲电氰基化反应

Scheme 30. Boron reagents mediated electrophilic cyanation of ketones

图式31. 烯丙基硼化合物的亲电氰基化反应

Scheme 31. Electrophilic cyanation of allylic boranes

图式32. 路易斯酸催化酚的氰基化反应

Scheme 32. Lewis acid catalyzed cyanation of phenols

图式33. α-溴代羰基化合物的还原氰基化反应

Scheme 33. Reductive cyanation of α-bromocarbonyl compounds

图式34. N-Ts氰胺与腈氧化物的[3+2]环加成反应

Scheme 34. [3+2] annulation of N-Ts cyanamides and nitrile oxides

图式35. N-Ts氰胺与腈亚胺的[3+2]环加成反应

Scheme 35. [3+2] annulation of N-Ts cyanamides and nitrile imines

图式36. N-Ts氰胺与α-卤代酰胺的[3+2]环加成反应

Scheme 36. [3+2] annulation of N-Ts cyanamides and α?haloamides

图式37. N-Ts氰胺与氮杂环丙烷的[3+2]环加成反应

Scheme 37. [3+2] annulation of N-Ts cyanamides and aziridines

图式38. 醇的脱氧氰胺化反应

Scheme 38. Deoxycyanamidation of alcohols

图式39. 钴催化N-Ts氰胺参与的转磺酰基反应

Scheme 39. Cobalt-catalyzed sulfonyl transfer of N-Ts cyanamides

图式40. N-Ts氰胺参与的环化反应

Scheme 40. Cyclization reaction involving N-Ts cyanamide

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