过渡金属催化碳二亚胺环化的研究进展

doi:10.6023/cjoc202010020

摘要/Abstract

碳二亚胺是合成含氮分子最有效的前体之一. 过渡金属催化的碳二亚胺环化反应已成为合成杂环产物的有效方法, 并引起了合成化学和药物化学家的极大关注. 近些年发表的大量成果证明了该合成方法在现代有机合成中的重要性. 总结了该领域在过去十年中的研究进展及一些开拓性的工作. 根据不同的环化机理, 从三部分归纳和讨论了从碳二亚胺到系列杂环分子的合成方法, 主要包括由亲核过程引发的串联环化、基于碳二亚胺对环金属中间体插入过程的环化和含不饱和体系的碳二亚胺参与的协同环化.

关键词: 碳二亚胺, 过渡金属催化, 环化, 杂环, 杂累积双烯

Carbodiimide is one of the most efficient precursors to the synthesis of N-containing molecules. Transition-metal- catalyzed cyclization of carbodiimides has become a powerful approach to heterocyclic products, and attracts considerable attention from synthetical and pharmaceutical chemists. The significant amount of documents that were published during the last years proves the importance of this approach in modern organic synthesis. The development of this field over last decade and some pioneering work are summarized. An array of synthetic methods for privileged heterocycles from carbodiimides are presented according to mechanically distinctive processes: cascade cyclization initiated by nucleophilic process, catalytic cyclization via the insertion of carbodiimides into metal-cycle intermediates and annulation of tethered carbodiimides with unsaturated systems.

Key words: carbodiimide, transition-metal-catalysis, cyclization, heterocycle, heterocumulene

引用此文

张震, 畅温旭. 过渡金属催化碳二亚胺环化的研究进展[J]. 有机化学, 2021, 41(5): 1835-1850.

Zhen Zhang, Wenxu Chang. Progress in Transition-Metal-Catalyzed Cyclization of Carbodiimides[J]. Chinese Journal of Organic Chemistry, 2021, 41(5): 1835-1850.

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图/表 43

图式1. 过渡金属催化碳二亚胺环化的不同反应路径

Scheme 1. Transition-metal-catalyzed cyclization of carbodiimides via distinctive paths

图式2. 碳二亚胺中官能团参与环化反应的基本策略

Scheme 2. Strategy of cascade cyclization with group in carbodiimide

图式3. Cu(I)催化的串联环化反应合成2-杂苯并咪唑

Scheme 3. Cu(I)-catalyzed cascade cyclization to synthesize 2-heterobenzimidazoles

图式4. Cu(II)催化的串联环化反应合成苯并咪唑或喹唑啉

Scheme 4. Cu(II)-catalyzed cascade cyclization to synthesize benzimidazoles or quinazolines

图式5. Ag(I)催化的区域选择性环化合成吲哚N-羧酰亚胺或N-羧酰亚胺

Scheme 5. Ag(I)-catalyzed regioselective cyclization to synthesize indole N-carboximidamides or N-carboximidoates

图式6. Cu(I)催化的催化一锅合成2-偶氮咪唑衍生物

Scheme 6. Cu(I)-catalyzed one-pot synthesis of 2-azolylimidazole derivatives

图式7. Pd催化串联加成/环羰基化反应合成2-杂喹唑啉-4(3H)-酮

Scheme 7. Tandem Pd-catalyzed addition/cyclocarbonylation to synthesize 2-heteroquinazolin-4(3H)-ones

图式8. Pd催化三组分反应合成喹唑啉-4(3H)-亚胺和4-亚氨基-3,4-二氢喹唑啉-2-基膦酸酯

Scheme 8. Pd-catalyzed three-component reaction to synthesize quinazolin-4(3H)-imines and 4-imino-3,4-dihydroquinazolin-2- ylphosphonates

图式9. 亲核试剂中官能团参与环化反应的基本策略

Scheme 9. Strategy of cascade cyclization with the functional group in nucleophile

图式10. Pd催Pd(0)催化的乙烯基氧杂环戊烷与碳二亚胺的环加成反应

Scheme 10. Pd(0)-catalyzed cycloaddition of vinyloxiranes with carbodiimides

图式11. Pd催化碳二亚胺环化合成2-乙烯基氮丙啶或2-乙烯基吡咯烷

Scheme 11. Pd-catalyzed cyclization to synthesize 2-vinyl- aziridines or 2-vinylpyrrolidines with carbodiimides

图式12. 无配体Cu(I)催化邻卤代苯酚或邻卤代苯胺与碳二亚胺的环化反应

Scheme 12. Ligand-free Cu(I)-catalyzed cascade reaction of o-halophenols or o-haloanilines with carbodiimides

图式13. Cu催化碳二亚胺与苯甲酸衍生物的多米诺反应

Scheme 13. Cu-catalyzed domino reaction of carbodiimides and benzoic acid derivatives

图式14. Cu(I)催化α-羟基酮和碳二亚胺的多米诺反应合成2-亚氨基-1,3-噁唑啉

Scheme 14. Cu(I)-catalyzed domino reaction of α-hydroxy- ketones and carbodiimide to synthesize 2-imino-1,3-oxazoline

图式15. Pd邻碘苯胺与碳二亚胺的环羰基化反应

Scheme 15. Pd-catalyzed cyclocarbonylation of o-iodoanilines with carbodiimides

图式16. Zn(OTf)2催化的氨基酸酯和碳二亚胺的环胍化/酰胺化

Scheme 16. Zn(OTf)2-catalyzed guanylation/amidation of amino acid esters and carbodiimides

图式17. Zn(OTf)2, La[N(SiMe3)2]3和咪唑啉-2-亚氨基钛引发剂催化碳二亚胺的胍化/环化

Scheme 17. Zn(OTf)2, La[N(SiMe3)2]3 and imidazolin-2-iminato titanium initiator catalyzed guanylation/cyclization

图式18. Cu催化的碳二亚胺、炔烃和二芳基碘鎓盐的串联环化

Scheme 18. Cu-catalyzed cascade annulation of carbodiimides, alkynes and diaryliodonium salts

图式19. Pd(0)/Fe(III)连续催化偶联/环化一锅法合成氨基四唑

Scheme 19. Sequential Pd(0)/Fe(III)-catalyzed coupling/cycli- zation to synthesize aminotetrazoles in one-pot fashion

图式20. 两底物所含官能团参与环化反应的基本策略

Scheme 20. Strategy of cascade cyclization with the functional group in both carbodiimide and nucleophile

图式21. Pd催化碳二亚胺与胺、CO或异腈的多组分串联环化反应

Scheme 21. Pd-catalyzed cascade cyclization of carbodiimides, amines with CO or isocyanides

图式22. Cu(I)催化的碳二亚胺和异氰基乙酸酯的串联环化反应

Scheme 22. Cu(I)-catalyzed tandem reaction of carbodiimides and isocyanoacetates

图式23. Cu(I)催化双(邻卤代芳基)碳二亚胺与吡咯衍生物的多米诺反应

Scheme 23. Cu(I)-catalyzed domino reaction of bis(o-haloaryl)carbodiimides and azole derivatives

图式24. Cu(I)催化双(邻卤代芳基)碳二亚胺与活性亚甲基化合物的多米诺反应

Scheme 24. Cu(I)-catalyzed domino reaction of bis-(o-haloaryl)carbodiimides and active methylene compounds

图式25. Cu(I)催化邻卤代芳基碳二亚胺与炔丙基胺的多米诺反应

Scheme 25. Cu(I)-catalyzed domino reaction of o-haloarylcarbodiimides and propargylic amines

图式26. Cu(I)催化的邻烯基苯基碳二亚胺与异氰酸酯的级联反应

Scheme 26. Cu(I)-catalyzed cascade reaction of o-alkenylphenyl carbodiimides with isocyanides

图式27. Co或Ni催化二苯基碳二亚胺与炔烃的三聚环化反应

Scheme 27. Co or Ni-catalyzed cyclotrimerization of acetylenes with carbodiimides

图式28. Co催化微波条件下固相合成稠合吡啶环化合物

Scheme 28. Co-catalyzed microwave-mediated solid-supported formation of fused pyridine rings

图式29. Rh催化碳二亚胺与二炔的[2+2+2]环加成反应

Scheme 29. Rh-catalyzed [2+2+2] cycloaddition of diynes with carbodiimides

图式30. Rh催化碳二亚胺与4-炔基醛的[4+2]环加成反应

Scheme 30. Rh-catalyzed [4+2] annulations of 4-alkynals with carbodiimides

图式31. Fe(CO)5催化碳二亚胺、炔烃和CO的[2+2+1]环加成反应

Scheme 31. Fe(CO)5-catalyzed [2+2+1] cycloaddition of alkyne, carbodiimide and CO

图式32. Ni催化碳二亚胺与靛红酸酐的脱羧环化反应

Scheme 32. Ni-catalyzed decarboxylative cyclization of isatoic anhydrides with carbodiimides

图式33. Rh催化戊烯基碳二亚胺与末端炔的[2+2+2]环加成反应

Scheme 33. Rh-catalyzed [2+2+2] cycloaddition of pentenyl carbodiimides with terminal alkynes

图式34. Rh催化乙烯基叠氮与异腈和炔烃/苯炔的级联反应

Scheme 34. Rh-catalyzed cascade reaction of vinyl azides with isonitriles and alkynes/benzynes

图式35. Rh催化经由乙烯基碳二亚胺中间体的双异腈插入反应

Scheme 35. Rh-catalyzed double isocyanides insertion via a vinylcarbodiimide intermediate

图式36. Pd催化含1,3-二烯碳二亚胺的分子内碳硼环化反应

Scheme 36. Pd-catalyzed intramolecular carboborylation of car- bodiimides bearing 1,3-diene

图式37. 炔基碳二亚胺与CO的Aza-Pauson-Khand反应的基本过程

Scheme 37. General process of catalytic Aza-Pauson-Khand reaction of alkyne carbodiimide with CO

图式38. 过渡金属参与的分子内炔基碳二亚胺的Pauson- Khand型反应

Scheme 38. Transition-metal-mediated intramolecular alkyne- carbodiimide Pauson-Khand-type reaction

图式39. Co2(CO)8催化炔基碳二亚胺的分子内Pauson-Khand型反应合成(±)-毒扁豆碱

Scheme 39. Co2(CO)8-catalyzed intramolecular Pauson-Khand- type reaction of alkyne carbodiimide for the synthesis of (±)- physostigmine

图式40. Rh(I)催化炔基碳二亚胺的Pauson-Khand型反应合成吡咯并[2,3-b]喹啉

Scheme 40. Rh(I)-catalyzed Pauson-Khand-type reaction of alkyne carbodiimide to synthesize pyrrolo[2,3-b]quinolines

图式41. Rh(I)催化双(炔丙基苯基)-碳二亚胺的分子内[2+ 2+2]环加成

Scheme 41. Rh(I)-catalyzed intramolecular [2+2+2] cycloaddition of bis(propargylphenyl)-carbodiimides

图式42. Rh(I)催化的N-[2-(2-炔-1-基)苯基]碳二亚胺的“烯型”环异构化

Scheme 42. Rh(I)-catalyzed “ene-type” cycloisomerization of N-[2-(2-alkyn-1-yl)phenyl] carbodiimides

图式43. Rh(I)连续催化炔基叠氮与两分子σ供体/π受体(异腈或CO)的串联环化反应

Scheme 43. Self-relay Rh(I)-catalyzed cyclization of alkyne-azides with two σ-donor/π-acceptor (isonitriles or CO)

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