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A Historic Overview of the Metal-Catalyzed Cross-Coupling Reactions

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Applied Cross-Coupling Reactions

Part of the book series: Lecture Notes in Chemistry ((LNC,volume 80))

Abstract

The main focus of this publication is the innovation of new synthetic reactions that can form various carbon–carbon bonds with high selectivity. The use of transition-metal-catalyzed cross-coupling reactions of organic electrophiles with organometallic nucleophiles started with the discovery of Kumada–Tamao–Corriu coupling in 1972—the reaction of organic halides and organomagnesium compounds under nickel catalysis. Combining fragments with a series of carbon centers into one segment, the transition-metal-catalyzed cross-coupling reactions have long been industrially utilized toward the synthesis of functional materials such as agricultural chemicals, pharmaceuticals, and polymers.

The original version of this chapter was revised: There was a change in the first name of the contributor in Chap. 1. The erratum to this chapter is available at DOI 10.1007/978-3-642-32368-3_9

An erratum to this chapter can be found at http://dx.doi.org/10.1007/978-3-642-32368-3_9

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References

  1. Tsuji J, Takahashi H (1965) Organic syntheses by means of noble metal compounds. XII.1 Reaction of the cyclooctadiene-palladium chloride complex with ethyl malonate. J Am Chem Soc 87:3275–3276

    Article  CAS  Google Scholar 

  2. Tsuji J, Tanaka H, Morikawa M (1965) Organic syntheses by means of noble metal compounds. XVII. Reaction of π-allylpalladium chloride with nucleophiles. Tetrahedron Lett, 4387–4388

    Google Scholar 

  3. Trost BM, Fullerton TJ (1973) New synthetic reactions Allylic alkylation. J Am Chem Soc 95:292–294

    Article  CAS  Google Scholar 

  4. Tsuji J (1969) Carbon-carbon bond formation via palladium complexes. Acc Chem Res 2:144–152

    Article  CAS  Google Scholar 

  5. Trost BM, Van Vranken DL (1996) Asymmetric transition metal-catalyzed allylic alkylations. Chem Rev 96:395–422

    Article  CAS  Google Scholar 

  6. Mizoroki T, Mori K, Ozaki A (1971) Arylation of olefin with aryl iodide catalyzed by palladium. Bull Chem Soc Jpn 44:581–581

    Article  CAS  Google Scholar 

  7. Heck RF, Nolley JP Jr (1972) Palladium-catalyzed vinylic hydrogen substitution reactions with aryl, benzyl, and styryl halides. J Org Chem 37:2320–2322

    Article  CAS  Google Scholar 

  8. Heck RF (1982) Palladium-catalyzed vinylation of organic halides. Org React 27:345–390

    CAS  Google Scholar 

  9. Hermann WA, Brossmer C, Öfele K, Reisinger CP, Priermeier T, Beller M, Fischer H (1995) Palladacycles as structurally defined catalysts for the Heck olefination of chloro- and bromoarenes. Angew Chem Int Ed Engl 34:1844–1848

    Article  Google Scholar 

  10. Xu L, Chen W, Xiao J (2000) Heck reaction in ionic liquids and the in situ identification of N-heterocyclic carbene complexes of palladium. Organometallics 19:1123–1127

    Article  CAS  Google Scholar 

  11. Stambuli JP, Stauffer SR, Shaughnessy KH, Hartwig JF (2001) Screening of homogeneous catalysts by fluorescence resonance energy transfer. Identification of catalysts for room-temperature Heck reactions. J Am Chem Soc 123:2677–2678

    Article  CAS  Google Scholar 

  12. Littke AF, Hartwig JF (2001) A versatile catalyst for Heck reactions of aryl chlorides and aryl bromides under mild conditions. J Am Chem Soc 123:6989–7000

    Article  CAS  Google Scholar 

  13. Morita DK, Stille JK, Norton JR (1995) Methyl/phenyl exchange between palladium and a phosphine ligand, consequences for catalytic coupling reactions. J Am Chem Soc 117:8576–8581

    Article  CAS  Google Scholar 

  14. Goodson FE, Wallow TI, Novak BN (1997) Mechanistic studies on the aryl-aryl interchange reaction of ArPdL2I (L = triarylphosphine) complexes. J Am Chem Soc 119:12441–12453

    Article  CAS  Google Scholar 

  15. Stanforth SP (1988) Catalytic cross-coupling reactions in biaryl synthesis. Tetrahedron 54:263–303

    Article  Google Scholar 

  16. Corriu RJP, Masse JP (1972) Activation of Grignard reagent by transition-metal complexes. A new and simple synthesis of trans-stilbenes and polyphenyls, J Chem Soc Chem Commun, 144

    Google Scholar 

  17. Kharasch MS, Fuchs CF (1943) Factors influencing the course and mechanisms of Grignard reactions. XI. The effect of metallic halides on the reaction of Grignard reagents with vinyl halides and substituted vinyl halides. J Am Chem Soc 65:504–507

    Article  CAS  Google Scholar 

  18. Tamura M, Kochi JK (1971) Vinylation of Grignard reagent. Catalysis by iron. J Am Chem Soc 93:1487–1489

    Article  CAS  Google Scholar 

  19. Tamao K, Sumitani K, Kumada M (1972) Selective carbon-carbon bond formation by cross-coupling of Grignard reagents with organic halides. Catalysis by nickel-phosphine complexes. J Am Chem Soc 94:4374–4376

    Article  CAS  Google Scholar 

  20. Uchino M, Yamamoto A, Ikeda S (1970) Preparation of a phenyl—nickel complex, phenyl(dipyridyl)nickel chloride, an olefin dimerization catalyst. J Organomet Chem 24:C63–C64

    Article  CAS  Google Scholar 

  21. Tamao K, Kiso Y, Sumitani K, Kumada M (1972) Alkyl group isomerization in the cross-coupling reaction of secondary alkyl Grignard reagents with organic halides in the presence of nickel-phosphine complexes as catalysts. J Am Chem Soc 94:9268–9269

    Article  CAS  Google Scholar 

  22. Saeki T, Takashima Y, Tamao K (2005) Nickel- and palladium-catalyzed cross-coupling reaction of polyfluorinated arenes and alkenes with Grignard reagents. Synlett, 1771–1774

    Google Scholar 

  23. Consiglio G, Botteghi C (1973) Stereoselektive Bildung der C-C-Bindung in der Kopplungsreaktion zwischen sek. Alkylmagnesiumbromiden und ungesättigten Halogeniden: asymmetrische Induktion durch einen optisch aktiven Diphosphin-Nickel-Komplex. Helv Chim Acta 56:460–463

    Article  CAS  Google Scholar 

  24. Kiso Y, Tamao K, Miyake N, Yamamoto K, Kumada M (1974) Asymmetric cross-coupling reaction of sec-alkyl Grignard reagents with organic halides in the presence of a chiral phosphine-nickel complex as a catalyst. Tetrahedron Lett 15:3–6

    Google Scholar 

  25. Hayashi T, Tajika M, Tamao K, Kumada M (1976) High stereoselectivity in asymmetric Grignard cross-coupling catalyzed by nickel complexes of chiral (aminoalkylferrocenyl) phosphines. J Am Chem Soc 98:3718–3719

    Article  CAS  Google Scholar 

  26. Kumada M, Tamao K, Sumitani K (1978) Phosphine-nickel complex catalyzed cross-coupling of Grignard reagents with aryl and alkenyl halides:1,2-dibutylbenzene. Org Synth 58:127–133

    Article  CAS  Google Scholar 

  27. Banno T, Hayakawa Y, Umeno M (2002) Some applications of the Grignard cross-coupling reaction in the industrial field. J Organomet Chem 653:288–291

    Article  CAS  Google Scholar 

  28. Terao J, Kambe N (2008) Cross-coupling reaction of alkyl halides with Grignard reagents catalyzed by Ni, Pd, or Cu complexes with π-carbon ligand(s). Acc Chem Res 41:1545–1554

    Article  CAS  Google Scholar 

  29. Vechorkin O, Proust V, Hu X (2009) Functional group tolerant Kumada-Corriu-Tamao coupling of nonactivated alkyl halides with aryl and heteroaryl nucleophiles: catalysis by a nickel pincer complex permits the coupling of functionalized Grignard reagents. J Am Chem Soc 131:9756–9766

    Article  CAS  Google Scholar 

  30. Yoshikai N, Matsuda H, Nakamura E (2008) Ligand exchange as the first irreversible step in the nickel-catalyzed cross-coupling reaction of Grignard reagents. J Am Chem Soc 130:15258–15259

    Article  CAS  Google Scholar 

  31. Yoshikai N, Matsuda H, Nakamura E (2009) Hydroxyphosphine ligand for nickel-catalyzed cross-coupling through nickel/magnesium bimetallic cooperation. J Am Chem Soc 131:9590–9599

    Article  CAS  Google Scholar 

  32. Yamamura M, Moritani I, Murahashi S (1975) The reaction of σ-vinylpalladium complexes with alkyllithiums. Stereospecific syntheses of olefins from vinyl halides and alkyllithiums. J Organomet Chem 91:C39–C42

    Article  CAS  Google Scholar 

  33. Murahashi S, Yamamura M, Yanagisawa K, Mita N, Kondo K (1979) Stereoselective synthesis of alkenes and alkenyl sulfides from alkenyl halides using palladium and ruthenium catalysts. J Org Chem 44:2408–2417

    Article  CAS  Google Scholar 

  34. Murahashi S, Naota T, Tanigawa Y (1984) Palladium-phosphine-complex-catalyzed reaction of organolithium compounds and alkenyl halides: (Z)-β-[2-(N, N-dimethylamino)phenyl]styrene. Org Synth 62:39–47

    Article  CAS  Google Scholar 

  35. Murahashi S (2002) Palladium-catalyzed cross-coupling reaction of organic halides with Grignard reagents, organolithium compounds and heteroatom nucleophiles. J Organomet Chem 653:27–33

    Article  CAS  Google Scholar 

  36. Nagaki A, Kenmoku A, Moriwaki Y, Hayashi A, Yoshida J (2010) Cross-coupling in a flow microreactor: Space integration of lithiation and Murahashi coupling. Angew Chem Int Ed 49:7543–7547

    Article  CAS  Google Scholar 

  37. Sonogashira K, Tohda Y, Hagihara N (1975) A convenient synthesis of acetylenes: catalytic substitutions of acetylenic hydrogen with bromoalkenes, iodoarenes and bromopyridines. Tetratedron Lett 16:4467–4470

    Article  Google Scholar 

  38. Cassar L (1975) Synthesis of aryl- and vinyl-substituted acetylene derivatives by the use of nickel and palladium complexes. J Organomet Chem 93:253–257

    Article  CAS  Google Scholar 

  39. Dieck HA, Heck RF (1975) Palladium catalyzed synthesis of aryl, heterocyclic and vinylic acetylene derivatives. J Organomet Chem 93:259–263

    Article  CAS  Google Scholar 

  40. Sonogashira K, Yatake T, Tohda Y, Takahashi S, Hagihara N (1977) Novel preparation of σ-alkynyl complexes of transition metals by copper(I) iodide-catalysed dehydrohalogenation. J Chem Soc Chem Commun, 291–292

    Google Scholar 

  41. Sonogashira K, Takahashi S, Hagihara N (1977) A new extended chain polymer, poly[trans-bis(tri-n-butylphosphine)platinum 1,4-butadiynediyl]. Macromolecules 10:879–880

    Article  CAS  Google Scholar 

  42. Sonogashira K (2002) Development of Pd–Cu catalyzed cross-coupling of terminal acetylenes with sp2-carbon halides. J Organomet Chem 653:46–49

    Article  CAS  Google Scholar 

  43. Chinchilla R, Nájera C (2007) The Sonogashira reaction: a booming methodology in synthetic organic chemistry. Chem Rev 107:874–922

    Article  CAS  Google Scholar 

  44. Heravi MM, Sadjadi S (2009) Recent advances in the application of the Sonogashira method in the synthesis of heterocyclic compounds. Tetrahedron 65:7761–7775

    Article  CAS  Google Scholar 

  45. Chinchilla R, Nájera C (2011) Recent advances in Sonogashira reactions. Chem Soc Rev 40:5084–5121

    Article  CAS  Google Scholar 

  46. Negishi E, Baba S (1976) Novel stereoselective alkenyl-aryl coupling via nickel-catalysed reaction of alkenylalanes with aryl halides. J Chem Soc Chem Commun, 596–597

    Google Scholar 

  47. Baba S, Negishi E (1976) A novel stereospecific alkenyl-alkenyl cross-coupling by a palladium- or nickel-catalyzed reaction of alkenylalanes with alkenyl halides. J Am Chem Soc 98:6729–6731

    Article  CAS  Google Scholar 

  48. Negishi E (1978) Selective carbon-carbon bond formation via transition metal catalysis: is nickel or palladium better than copper? In: Brewster JH (ed) Aspects of mechanism and organometallic chemistry. Plenum Press, New York

    Google Scholar 

  49. Negishi E, Van Horn DE (1977) Selective carbon-carbon bond formation via transition metal catalysis. 4. A novel approach to cross-coupling exemplified by the nickel-catalyzed reaction of alkenylzirconium derivatives with aryl halides. J Am Chem Soc 99:3168–3170

    Article  CAS  Google Scholar 

  50. Okukado N, Van Horn DE, Klima WL, Negishi E (1978) A highly stereo-, regio-, and chemoselective synthesis of conjugated dienes by the palladium-catalyzed reaction of (E)-1-alkenylzirconium derivatives with alkenyl halides. Tetrahedron Lett 19:1027–1030

    Article  Google Scholar 

  51. King AO, Okukado N, Negishi E (1977) Highly general stereo-, regio-, and chemo-selective synthesis of terminal and internal conjugated enynes by the Pd-catalysed reaction of alkynylzinc reagents with alkenyl halides. J Chem Soc Chem Commun, 683–684

    Google Scholar 

  52. Negishi E, King AO, Okukado N (1977) Selective carbon-carbon bond formation via transition metal catalysis. 3. A highly selective synthesis of unsymmetrical biaryls and diarylmethanes by the nickel- or palladium-catalyzed reaction of aryl- and benzylzinc derivatives with aryl halides. J Org Chem 42:1821–1823

    Article  CAS  Google Scholar 

  53. Negishi E (1982) Palladium- or nickel-catalyzed cross coupling. A new selective method for carbon-carbon bond formation. Acc Chem Res 15:340–348

    Article  CAS  Google Scholar 

  54. Erdik E (1992) Transition metal catalyzed reactions of organozinc reagents. Tetrahedron 48:9577–9648

    Article  CAS  Google Scholar 

  55. Huang Z, Qian M, Babinski DJ, Negishi E (2005) Palladium-Catalyzed Cross-Coupling Reactions with Zinc, Boron, and Indium Exhibiting High Turnover Numbers (TONs): use of Bidentate Phosphines and Other Critical Factors in Achieving High TONs. Organometallics 24:475–478

    Article  CAS  Google Scholar 

  56. Negishi E, Hu Q, Huang Z, Qian M, Wang G (2005) Palladium-catalyzed alkenylation by the Negishi coupling. Aldrichimica Acta 38:71–88

    CAS  Google Scholar 

  57. Zhu G, Negishi E (2008) 1,4-Pentenyne as a five-carbon synthon for efficient and selective syntheses of natural products containing 2,4-dimethyl-1-penten-1,5-ylidene and related moieties by means of Zr-catalyzed carboalumination of alkynes and alkenes. Chem Eur J 14:311–318

    Article  CAS  Google Scholar 

  58. Wang G, Mohan S, Negishi E (2011) Highly selective synthesis of conjugated dienoic and trienoic esters via alkyne elementometalation-Pd-catalyzed cross-coupling. Proc Natl Acad Sci USA 108:11344–11349

    Article  CAS  Google Scholar 

  59. Kosugi M, Sasazawa K, Shimizu Y, Migita T (1977) Reactions of allyltin compounds allylation of aromatic halides with allyltributyltin in the presence of tetrakis(triphenylphosphine)palladium(0). Chem Lett, 301–302

    Google Scholar 

  60. Milstein D, Stille JK (1978) A general, selective, and facile method for ketone synthesis from acid chlorides and organotin compounds catalyzed by palladium. J Am Chem Soc 100:3636–3638

    Article  CAS  Google Scholar 

  61. Milstein D, Stille JK (1979) Palladium-catalyzed coupling of tetraorganotin compounds with aryl and benzyl halides. Synthetic utility and mechanism. J Am Chem Soc 101:4992–4998

    Article  CAS  Google Scholar 

  62. Miyaura N, Suzuki A (1979) Stereoselective synthesis of arylated (E)-alkenes by the reaction of alk-1-enylboranes with aryl halides in the presence of palladium catalyst. J Chem Soc Chem Commun, 866–867

    Google Scholar 

  63. Miyaura N, Yamada K, Suzuki A (1979) A new stereospecific cross-coupling by the palladium-catalyzed reaction of 1-alkenylboranes with 1-alkenyl or 1-alkynyl halides. Tetrahedron Lett 20:3437–3440

    Article  Google Scholar 

  64. Miyaura N, Suzuki A (1995) Palladium-catalyzed cross-coupling reactions of organoboron compounds. Chem Rev 95:2457–2483

    Article  CAS  Google Scholar 

  65. Miyaura N, Yanagi T, Suzuki A (1981) The palladium-catalyzed cross-coupling reaction of phenylboronic acid with haloarenes in the presence of bases. Synth Commun 11:513–519

    Article  CAS  Google Scholar 

  66. Molander GA, Canturk B (2009) Organotrifluoroborates and monocoordinated palladium complexes as catalysts—a perfect combination for Suzuki–Miyaura coupling. Angew Chem Int Ed 48:9240–9261

    Article  CAS  Google Scholar 

  67. Billinsley KL, Bachwald SL (2008) A general and efficient method for the Suzuki–Miyaura coupling of 2-pyridyl nucleophiles. Angew Chem Int Ed 47:4695–4698

    Article  Google Scholar 

  68. Cammidge AN, Goddard VHM, Gopee H, Harrison NL, Hughes DL, Schubert CJ, Sutton BM, Watts GL, Whitehead AJ (2006) Aryl trihydroxyborates: easily isolated discrete species convenient for direct application in coupling reactions. Org Lett 8:4071–4074

    Article  CAS  Google Scholar 

  69. Yamamoto Y, Takizawa M, Yu XQ, Miyaura N (2008) Cyclic triolborates: air- and water-stable ate complexes of organoboronic acids. Angew Chem Int Ed 47:928–931

    Article  CAS  Google Scholar 

  70. Yamamoto Y, Takizawa M, Yu XQ, Miyaura N (2010) Palladium-catalyzed cross-coupling reaction of heteroaryltriolborates with aryl halides for synthesis of biaryls. Heterocycles 80:359–368

    Article  CAS  Google Scholar 

  71. Noguchi H, Hojo K, Suginome M (2007) Boron-masking strategy for the selective synthesis of oligoarenes via iterative Suzuki-Miyaura coupling. J Am Chem Soc 129:758–759

    Article  CAS  Google Scholar 

  72. Gillis EP, Burke MD (2007) A simple and modular strategy for small molecule synthesis: Iterative Suzuki-Miyaura coupling of B-protected haloboronic acid building blocks. J Am Chem Soc 129:6716–6717

    Article  CAS  Google Scholar 

  73. Yoshida J, Tamao K, Yamamoto H, Kakui T, Uchida T, Kumada M (1982) Organofluorosilicates in organic synthesis. 14. Carbon-carbon bond formation promoted by palladium salts. Organometallics 1:542–549

    Article  CAS  Google Scholar 

  74. Hatanaka Y, Hiyama T (1988) Cross-coupling of organosilanes with organic halides mediated by a palladium catalyst and tris(diethylamino)sulfonium difluorotrimethylsilicate. J Org Chem 53:918–920

    Article  CAS  Google Scholar 

  75. Denmark SE, Sweis RF (2001) Fluoride-free cross-coupling of organosilanols. J Am Chem Soc 123:6439–6440

    Article  CAS  Google Scholar 

  76. Nakao Y, Imanaka H, Sahoo AK, Yada A, Hiyama T (2005) Alkenyl- and aryl[2-(hydroxymethyl)phenyl]dimethylsilanes: an entry to tetraorganosilicon reagents for the silicon-based cross-coupling reaction. J Am Chem Soc 127:6952–6953

    Article  CAS  Google Scholar 

  77. Nakao Y, Hiyama T (2011) Silicon-based cross-coupling reaction: an environmentally benign version. Chem Soc Rev 40:4893–4901

    Article  CAS  Google Scholar 

  78. Paul F, Hartwig JF (1994) Palladium-catalyzed formation of carbon-nitrogen bonds. Reaction intermediates and catalyst improvements in the hetero cross-coupling of aryl halides and tin amides. J Am Chem Soc 116:5969–5970

    Article  CAS  Google Scholar 

  79. Hartwig JF (1998) Carbon-heteroatom bond-forming reductive eliminations of amines, ethers, and sulfides. Acc Chem Res 31:852–860

    Article  CAS  Google Scholar 

  80. Guram AS, Buchwald SL (1994) Palladium-catalyzed aromatic aminations with in situ generated aminostannanes. J Am Chem Soc 116:7901–7902

    Google Scholar 

  81. Surry DS, Buchwald SL (2008) Biaryl phosphane ligands in palladium-catalyzed amination. Angew Chem Int Ed 47:6338–6361

    Article  CAS  Google Scholar 

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  1. Division of Earth, Life, and Molecular Sciences, Graduate School of Natural Science and Technology, Okayama University, 3-1-1 Tsushimanaka, Kita-ku, Okayama, 700-8530, Japan

    Yasushi Nishihara

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  1. Department of Chemistry, Okayama University, Okayama, Japan

    Yasushi Nishihara

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Nishihara, Y. (2013). A Historic Overview of the Metal-Catalyzed Cross-Coupling Reactions. In: Nishihara, Y. (eds) Applied Cross-Coupling Reactions. Lecture Notes in Chemistry, vol 80. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-32368-3_1

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