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Mn-Catalyzed Cross-Coupling Reactions for Organic Synthesis

Explore manganese-catalyzed cross-coupling methods for forming C-C and C-X bonds in organic molecules. Learn about the mechanisms and examples involving organometallic compounds, Grignard reagents, aryl halides, and more. Discover the efficiency and versatility of Mn in modern organic synthesis.

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Mn-Catalyzed Cross-Coupling Reactions for Organic Synthesis

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  1. Mn-Catalyzed Cross-Coupling Mn Nian Li [Ar]3d54s2 20190513

  2. Lutz Ackermann, Chem. Rev. 2019, 119, 2192−2452

  3. Upper range of dietary intake for adults essential element essential element for all species (human daily intake ~ 4 mg) Lutz Ackermann, Chem. Rev. 2019, 119, 2192−2452

  4. Abundance of the chemical elements naturally abundant https://en.wikipedia.org/wiki/Abundance_of_the_chemical_elements

  5. Price of 3d transition metals (TMs) and common TMs in C−H activation in €/kg. accessed on 09/05/2018 low cost Lutz Ackermann, Chem. Rev. 2019, 119, 2192−2452

  6. Tolerance of transition metals in drugs. *High tolerance, exact amount could not be determined low toxicity Lutz Ackermann, Chem. Rev. 2019, 119, 2192−2452

  7. Mn-Catalyzed Cross-Coupling outline 1. Mn-catalyzed cross-coupling for C-C bond formation 2. Mn-catalyzed cross-coupling for C-X bond formation

  8. Mn-Catalyzed Cross-Coupling 1. Mn-catalyzed cross-coupling for C-C bond formation • Coupling of organometallic for C-C bond formation

  9. 1.1 Coupling of organometallic for C-C bond formation The first Mn catalyzed homocoupling of alkenyllithium substrate Proposed Mechanism Cahiez, G.; Bernard, D.; Normant, J. F. J. Organomet. Chem. 1976, 113, 99.

  10. 1.1 Coupling of organometallic for C-C bond formation MnCl2-catalyzed homocoupling of Grignard reagents [A] G. Cahiez, A. Moyeux, C. Duplais, J. Am. Chem. Soc. 129 (2007) 13788–13789. [B] T. Truong, J. Alvarado, O. Daugulis, Org. Lett. 12 (2010) 1200–1203. [C] Z. Zhou, W. Xue, J. Organomet. Chem. 694 (2009) 599–603. [D] Y. Yuan, Y. Bian, Appl. Organometal. Chem. 22 (2008) 15–18

  11. 1.1 Coupling of organometallic for C-C bond formation MnCl2-catalyzed homocoupling of Grignard reagents oxygen-driven Mn-catalyzed homocoupling DCE-driven Mn-catalyzed homocoupling [A] G. Cahiez, A. Moyeux, C. Duplais, J. Am. Chem. Soc. 129 (2007) 13788–13789. [B] T. Truong, J. Alvarado, O. Daugulis, Org. Lett. 12 (2010) 1200–1203. [C] Z. Zhou, W. Xue, J. Organomet. Chem. 694 (2009) 599–603. [D] Y. Yuan, Y. Bian, Appl. Organometal. Chem. 22 (2008) 15–18

  12. 1.1 Coupling of organometallic for C-C bond formation MnCl2-catalyzed heterocoupling of Grignard reagents 2.5 eq G. Cahiez, C. Duplais, J. Buendia, Angew. Chem. Int. Ed. 48 (2009) 6731–6734.

  13. 1.1 Coupling of organometallic for C-C bond formation Mn-catalyzed homocoupling of organostannanes S.-K. Kang, T.-G. Baik, X.H. Jiao, Y.-T. Lee, Tetrahedron Lett. 40 (1999) 2383–2384.

  14. 1.1 Coupling of organometallic for C-C bond formation Mn-catalyzed Stillecoupling Inorganic salt control the homocoupling by-product sp2-sp3Coupling ? S.-K. Kang, J.-S. Kim, S.-C. Choi, J. Org. Chem. 62 (1997) 4208–4209.

  15. 1.1 Coupling of organometallic for C-C bond formation Mn-catalyzed cross-coupling of organostannanes with aryliodoniumsalts S.-K. Kang, W.-Y. Kim, Y.-T. Lee, S.-K. Ahn, J.-C. Kim, Tetrahedron Lett. 39 (1998) 2131–2132.

  16. 1.1 Coupling of organometallic for C-C bond formation Cross-coupling of Grignard reagents with organotellurides碲（4d105s25p4） Inversion E-configuration Retention Z-configuration M.S. Silva, R.S. Ferrarini, B.A. Sousa, F.T. Toledo, J.V. Comasseto, R.A. Gariani,Tetrahedron Lett. 53 (2012) 3556–3559.

  17. Mn-Catalyzed Cross-Coupling 1. Mn-catalyzed cross-coupling for C-C bond formation C-C bond formation via C-X activation

  18. 1.2 C-C bond formation via C-X activation First example of Mn-catalyzed cross-coupling reaction with arylhalogenides low yield anisole as a major component G. Cahiez, D. Bernard, J.F. Normant, J. Organomet. Chem. 113 (1976) 107–113.

  19. 1.2 C-C bond formation via C-X activation MnCl2-catalyzed cross-coupling of Grignard reagents with activated aryl halides electron-withdrawing group • G. Cahiez, F. Lepifre, P. Ramiandrasoa, Synthesis (1999) 2138–2144. ortho-ketone G. Cahiez, D. Luart, F. Lecomte, Org. Lett. 6 (2004) 4395–4398. F. Zhang, Z. Shi, F. Chen, Y. Yuan, Appl. Organometal. Chem. 24 (2010) 57–63..

  20. 1.2 C-C bond formation via C-X activation MnCl2-catalyzed cross-coupling of Grignard reagents with activated aryl halides nitrogen heterocyclic chlorides Selected example M. Rueping, W. Ieawsuwan, Synlett (2007) 247–250.

  21. 1.2 C-C bond formation via C-X activation MnCl2-catalyzed cross-coupling of Grignard reagents with alkenylhalides conjugated chloroenynesor dienes • M. Alami, P. Ramiandrasoa, G. Cahiez, Synlett (1998) 325–327. alkenylhalides G. Cahiez, O. Gager, F. Lecomte, Org. Lett. 10 (2008) 5255–5256.

  22. 1.2 C-C bond formation via C-X activation MnCl2-catalyzed cross-coupling of Grignard reagents with 1,1-dibromoalkanes Proposed Mechanism Synthesis of alkenylsilanes S. T.M. O.A. E. R.E. Chelation-assisted H. Kakiya, R. Inoue, H. Shinokubo, K. Oshima, Tetrahedron Lett. 38 (1997) 3275–3278.

  23. Mn-Catalyzed Cross-Coupling 1. Mn-catalyzed cross-coupling for C-C bond formation C-C bond formation via C-H activation

  24. 1.3 C-C bond formation via C-H activation stoichiometric C−H activation Bruce, M. I.; Iqbal, M. Z.; Stone, F. G. A. J. Chem. Soc. A 1970, 3204. directing groups So far, a variety of directing groups, which contain nitrogen,oxygen, and phosphorous functionalities • Lutz Ackermann, Chem. Rev. 2019, 119, 2192−2452

  25. 1.3 C-C bond formation via C-H activation Manganese(I)-Catalyzed C−H Addition to Aldehydes Proposed Mechanism R.E. O.A. Diastereo-control M.I. Kuninobu, Y.; Nishina, T.; Takeuchi, T.; Takai, K. Angew. Chem. Int. Ed. 2007, 46, 6518.

  26. 1.3 C-C bond formation via C-H activation Mn-Catalyzed C(sp2)-H Addition to Aldehydes and Nitriles Mn(I)-Cat. C−H Additions to Nitriles Silane-Free Mn(I)-Cat. C−H Additions to Aldehydes L.A. promoted Wang, C. Angew. Chem., Int. Ed. 2015, 54, 13659−13663

  27. 1.3 C-C bond formation via C-H activation Proposed Mechanism for Mn-Catalyzed C(sp2 )-H Addition to Aldehydes and Nitriles σ-bond metathesis Wang, C. Angew. Chem., Int. Ed. 2015, 54, 13659−13663

  28. 1.3 C-C bond formation via C-H activation Mn-Catalyzed Aromatic C−H Alkenylation with Terminal Alkynes L.B. promoted Zhou, B.; Chen, H.; Wang, C. J. Am. Chem. Soc. 2013, 135, 1264−1267

  29. 1.3 C-C bond formation via C-H activation Mn-Catalyzed Aromatic C−H Alkenylation with Terminal Alkynes the catalytic base is the key to success of this transformation exothermic step LLHT Wang, C. J. Am. Chem. Soc. 2013, 135, 1264

  30. 1.3 C-C bond formation via C-H activation Manganese(I)-Catalyzed C−H Allylation allyl carbonate Decarboxylative C−H/C−O Cleavages in Water Ackermann, Angew. Chem., Int. Ed. 2017, 56, 6339−6342. Ackermann, L. Angew. Chem., Int. Ed. 2016, 55, 7747−7750.

  31. 1.3 C-C bond formation via C-H activation Manganese(I)-Catalyzed C−H Cyanationof Heteroarenes tryptophans Liu, W.; Richter, S. C.; Mei, R.; Feldt, M.; Ackermann, L. Chem.- Eur. J. 2016, 22, 17958−17961.

  32. 1.3 C-C bond formation via C-H activation Manganese(I)-Catalyzed C−H Alkynylations with Bromoalkynes Amino acid moieties fully accepted Without loss of the enantiomeric Ruan, Z.; Sauermann, N.; Manoni, E.; Ackermann, L. Angew. Chem., Int. Ed. 2017, 56, 3172−3176.

  33. 1.3 C-C bond formation via C-H activation Manganese-Catalyzed C−H Arylation/Arylation Continuous Flow Photomediated • Ackermann, L. ACS Catal. 2018, 8, 4402−4407. Photo-Flow -Chemistry Nuhant, P. Angew. Chem.,Int. Ed. 2017, 56, 15309−15313.(594) Ackermann, L.Angew. Chem., Int. Ed. 2018, 57,10625−10629.

  34. Mn-Catalyzed Cross-Coupling 2. Mn-catalyzed cross-coupling for C-X bond formation

  35. 2.1 Mn-catalyzed C-N bond formation Mn- and Mn/Cu-catalyzed amination of aryl and heteroarylhalides Mn/Cu-catalyzed Mn-catalyzed Y.-C. Teo, F.-F. Yong, C.-Y. Poh, Y.-K. Yan, G.-L. Chua, Chem. Commun. (2009) 6258–6260. Y.-C. Teo, F.-F. Yong, G.S. Lim, Tetrahedron Lett. 52 (2011) 7171–7174.

  36. 2.1 Mn-catalyzed C-N bond formation Mn-catalyzed amination of aryl iodides with aliphatic amines F.-F. Yong, Y.-C. Teo, Tetrahedron Lett. 51 (2010) 3910–3912.

  37. 2.1 Mn-catalyzed C-N bond formation Mn/Cu Bimetallic Catalyst for N-Arylation of Amides and Sulfonamides in Water Y.-C. Teo, F.-F. Yong, I.K. Ithnin, S.-H. Trionna Yio, Z. Lin, Eur. J. Org. Chem. (2013) 515–524.

  38. 2.1 Mn-catalyzed C-N bond formation Cu/Mncatalyzed synthesis of diphenylamine Ligand-free aqueous medium D.-S.Sanghapal, Tetrahedron Letters 54 (2013) 5351–5354

  39. 2.2 Mn-catalyzed C-S bond formation Mn-catalyzedthiolation of vinyl and aryl iodides Phen RI = ect. M. Bandaru, N.M. Sabbavarpu, R. Katla, V.D.N. Yadavalli, Chem. Lett. 39 (2010) 1149–1151. T.-J. Liu, C.-L. Yi, C.-C. Chan, C.-F. Lee, Chem. Asian J. 8 (2013) 1029–1034.

  40. 2.3 Mn-catalyzed C-B bond formation Cu/Mncatalyzed synthesis of diphenylamine 450-Watt medium-pressure Hanoviamercury arc lamp Chen, H.; Hartwig, J. F. Angew. Chem. Int. Ed. 1999, 38, 3391

  41. 2.3 Mn-catalyzed C-B bond formation Manganese-Catalyzed Borylation of Unactivated Alkyl Chlorides (only works for alkyl Bromide) Atack, T. C.; Cook, S. P. J. Am. Chem. Soc. 2016, 138, 6139.

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