有机转化中二碘化钐及其他钐试剂近期发展研究

doi:10.6023/cjoc202011034

摘要/Abstract

钐试剂自被发现以来, 一直在有机合成中占据着一席之地. SmI₂优异的单电子转移能力和还原能力都具有重要的研究价值. Sm、allylSmBr、SmI₃等其他钐试剂的潜力也逐渐被开发出来. 综述了近5年来SmI₂以及其他钐试剂介入的反应. 主要分为三大部分: (1) SmI₂促进的偶联反应研究, (2)其他钐试剂(Sm, allylSmBr, SmI₃, Sm(OTf)₃)等促进的偶联反应研究, (3)钐试剂介入的有机还原反应.

关键词: 有机合成, 偶联反应, 还原反应, 二碘化钐, 钐试剂, 有机钐

Since the samarium diiodide was discovered, it has been occupying a key field in organic synthesis due to the excellent ability of both single electron transfer and reduction. Other samarium reagents have also been wildly developed in recent years, such as Sm, allylSmBr, SmI₃and so on. In this review, the reactions mediated by samarium reagents especially SmI₂ in latest five years are summarized. It mainly includes three parts: studies on the SmI₂ promoted coupling reactions, studies on the coupling reactions promoted by other samarium reagents (Sm, allylSmBr, SmI₃, Sm(OTf)₃ etc.), and studies on the samarium reagents promoted organic reduction reactions.

Key words: organic synthesis, coupling reactions, reductions, samarium diiodide, samarium reagents, organosamarium

引用此文

刘晨, 齐燕, 刘永军. 有机转化中二碘化钐及其他钐试剂近期发展研究[J]. 有机化学, 2021, 41(6): 2202-2216.

Chen Liu, Yan Qi, Yongjun Liu. Recent Development of Samarium Diiodide and Other Samarium Reagents in Organic Transformation[J]. Chinese Journal of Organic Chemistry, 2021, 41(6): 2202-2216.

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图/表 60

. (2) Pinacol偶联类型

. (3)亚胺及其衍生物偶联类型

. (4)无羰基类型

. (5) Grignard/Barbier类型

. (6) Reformatsky类型

. (7)羟醛类型

图式1. SmI2偶联反应类型综述

Scheme 1. Review of the coupling reactions of SmI2

图式2. Ryanodine的合成

Scheme 2. Synthetic Fig. of ryanodine

图式3. SmI2促进烯烃自由基环化串联反应

Scheme 3. SmI2-mediated radical cyclization cascade

图式4. 催化循环

Scheme 4. Catalytic cycle

图式5. 酯与DIBAL-H的自由基环化

Scheme 5. Ester with DIBAL-H and radical cyclization

图式6. 紫杉醇ABC环的构建

Scheme 6. Construction of ABC ring of paclitaxel

图式7. 硝酮与羰基化物还原偶联机理

Scheme 7. Mechanism for reductive coupling of nitrones and carbonyl compounds

图式8. 苯胺衍生物或杂芳胺与伯醇的烷基化

Scheme 8. Alkylation of aniline derivatives or alkylation of heteroaromatic amines with various primary alcohols

图式9. SmI2-H2O介入的酰亚胺的环化反应

Scheme 9. Cyclization of five-membered cyclic imides via aminoketyl radicals using SmI2-H2O

图式10. SmI2介入的取代醇的合成

Scheme 10. SmI2-mediated synthesis of substituted alcohol

图式11. 肟醚与SmI2的反应

Scheme 11. Reaction of oxime ethers with SmI2

图式12. α-芳基-α'-羟基酮的合成

Scheme 12. Synthesis of α-aryl-α'-hydroxy ketones

图式13. SmI2-LiBr介入还原偶联反应

Scheme 13. SmI2-LiBr mediated reductive coupling reactions

图式14. SmI2介入的螺环化反应

Scheme 14. SmI2-mediated spirocyclization reaction

图式15. 自由基环化

Scheme 15. Radical cyclization

图式16. 自由基环化的可能过渡态

Scheme 16. Plausible transition states of radical cyclization

图式17. SmI2介入的不对称合成

Scheme 17. SmI2 mediated asymmetric synthesis

图式18. SmI2促进的溴炔的自由基环化

Scheme 18. Radical cyclization of bromoalkyne with SmI2

图式19. 吡咯的合成

Scheme 19. Synthesis of pyrrole

图式20. 2,2'-黄酮的合成

Scheme 20. Synthesis of 2,2'-biflavanones

图式21. 炔烃氢硅烷化

Scheme 21. Hydrosilylation of alkynes

图式22. Pinacol偶联反应机理

Scheme 22. The transformation of Pinacol

图式23. 脂肪醛或酮的pinacol偶联

Scheme 23. Pinacol couplings of aliphatic aldehydes and ketones

图式24. 紫杉醇ABC环合成

Scheme 24. Construction of ABC ring of paclitaxel

图式25. Barbier反应

Scheme 25. The transformation of Barbier

图式26. SmI2促进的呋喃糖苷与环己酮或辛醛偶联

Scheme 26. SmI2-mediated furanosides coupling with cyclohexanone and octanal

图式27. Reformatsky反应机理

Scheme 27. The mechanism of Refomatsky

图式28. 分子内Reformatsky环化

Scheme 28. Intramolecular Reformatsky aldol cyclization

图式29. β-羟基酮的非对映选择羟乙基化

Scheme 29. Diastereoselective hydroxyethylation of β-hydroxyketones

图式30. SmI2促进的噁唑烷酮与萜烯烯醛的Reformatsky反应

Scheme 30. SmI2-mediated Reformatsky reaction of oxazolidinones with terpene enals

图式31. 三环[5.2.1.01.6]癸烯的合成

Scheme 31. Synthesis of tricyclo[5.2.1.01.6]decene

图式32. SmI2-H2O介入五元内酯环化

Scheme 32. SmI2-H2O in radical cyclization of five-membered lactones

图式33. SmI2介入二氢噻喃类化合物合成

Scheme 33. SmI2-mediated synthesis of dihydrothiochroman-ols

图式34. SmI2介入还原偶联二聚

Scheme 34. SmI2-mediated reductive coupling dimerization

图式35. SmI2促进羰游基烯烃环化

Scheme 35. SmI2-mediated desymmetrizing ketyl olefin cyclization

图式36. SmI2介入还原环化

Scheme 36. SmI2-mediated reductive cyclization

图式37. 苄基卤的偶联

Scheme 37. Homocoupling of benzyl halides

图式38. 多种醛和硝基烷烃的亨利反应

Scheme 38. Henry reactions with various aldehydes and nitroalkanes

图式39. 苯甲醛与丙烯酸酯或马来酸酐加成

Scheme 39. Addition of benzaldehydes to acrylates or maleates

图式40. 4Å分子筛促进甲醇生成

Scheme 40. Promotion of the formation of MeOH by 4Å molecular sieves

图式41. 多种有机卤化物的偶联

Scheme 41. The versatile homocoupling of organohalides

图式42. 烯丙基溴化钐促进的环化反应

Scheme 42. AllylSmBr mediated reaction of cyclization

图式43. 烯丙基溴化钐促进醛或酮发生还原偶联

Scheme 43. Reductive coupling of aldehydes or ketones with allylSmBr

图式44. 含氧双环[3.1.0]己烷-1-醇的合成

Scheme 44. Synthesis of oxobicyclo[3.1.0]hexane-1-ols

图式45. α-氧代酮的Michael加成

Scheme 45. Michael addition of α-oxy ketones

图式46. Sm(OTf)3催化对称二苯乙烯与叠氮化合物[2+2+1]环加成

Scheme 46. Sm(OTf)3 catalyzed [2+2+1] annulations of symmetric stilbenes with azidomethyl aromatics

图式47. 1-氧-3,6-硫杂环庚烷与氨基酸酯的环化反应

Scheme 47. Recyclization of 1-oxa-3,6-dithiacycloheptane with amino acid esters

图式48. SmI3-I2共同催化1,3-二羰基酯α-羟基化

Scheme 48. SmI3 and I2 co-catalyzed aerobic α-hydroxylation of 1,3-dicarbonyl esters

图式49. SmI3/CuI促进α-卤代酮偶联

Scheme 49. Reactions of α-haloketones promoted by SmI 3/CuI

图式50. 溴代、碘代芳香族或杂环化合物与醛或酮偶联反应

Scheme 50. Aromatic or heterocyclic iodides and bromides coupling with ketone or aldehydes

图式51. 硒代酰胺的还原反应

Scheme 51. Reduction of selenoamide

图式52. 烯胺还原反应

Scheme 52. Enamine reduction

图式53. 苯甲酸烯丙基酯还原反应

Scheme 53. Allylic benzoate reductions

图式54. 利用SmBr2脱保护基

Scheme 54. Deprotection using SmBr2

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