Pd-NHC (PEPPSI)
Complexes: Synthetic Utility and Computational Studies into Their
Reactivity

Michael G. Organ; Gregory A. Chass; De-Cai Fang; Alan C. Hopkinson; Cory Valente

doi:10.1055/s-2008-1067225

SPECIALTOPIC

Pd-NHC (PEPPSI) Complexes: Synthetic Utility and Computational Studies into Their Reactivity

Michael G. Organ*^a, Gregory A. Chass^b, De-Cai Fang^c, Alan C. Hopkinson^a, Cory Valente^a
^a Department of Chemistry, York University, 4700 Keele Street, Toronto, ON, M3J 1P3, Canada
e-Mail: organ@yorku.ca;
^b School of Chemistry, University of Wales, Bangor LL57 2UW, UK
^c College of Chemistry, Beijing Normal University, Beijing 100875, P. R. of China

Abstract

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Abstract

This review concentrates on the results obtained thus far in cross-coupling reactions utilising Pd-PEPPSI-IPr (pre)catalyst. Results from computational studies expose possible factors behind the high reactivity of this complex, as well as mechanistic details for the IPr-Pd-mediated alkyl-alkyl Negishi cross-coupling.

1 Introduction

2 Evolution to Pd-PEPPSI Complexes

2.1 Background of NHCs; Unraveling Electronic and Steric Components

2.2 Design and Preparation of Pd-PEPPSI Complexes

2.3 Mechanism of Activation and Role in the Catalytic Cycle

3 Cross-Coupling Results with Pd-PEPPSI Complexes

3.1 General Cross-Coupling Scheme

3.2 The Suzuki-Miyaura Reaction

3.3 The Kumada-Tamao-Corriu Reaction

3.4 The Negishi Reaction

3.5 Buchwald-Hartwig-Yagupol’skii Amination

4 Theory and Computation

4.1 Theory

4.2 Computation

4.3 Geometric Structure

4.4 Reaction Profile

4.5 Interactions

4.6 Atoms-in-Molecules

5 Conclusions

Key words

palladium - cross-coupling - PEPPSI - computation

Full Text

References

1 Herrmann WA. Angew. Chem. Int. Ed. 2002, 41: 1290

2 Kantchev EAB. O’Brien CJ. Organ MG. Angew. Chem. Int. Ed. 2007, 46: 2768

3 Kantchev EAB. O’Brien CJ. Organ MG. Aldrichimica Acta 2006, 39: 97

4 Herrmann WA. Öfele K. Preysing D.-v. Schneider SK. J. Organomet. Chem. 2003, 687: 229

5 O’Brien CJ. Kantchev EAB. Valente C. Hadei N. Chass GA. Lough A. Hopkinson AC. Organ MG. Chem. Eur. J. 2006, 12: 4743

6 Valente C. Baglione S. Candito D. O’Brien CJ. Organ MG. Chem. Commun. 2008, 735

7 Organ MG. Avola S. Dubovyk I. Hadei N. Kantchev EAB. O’Brien CJ. Valente C. Chem. Eur. J. 2006, 12: 4749

8 Organ MG. Abdel-Hadi M. Avola S. Hadei N. Nasielski J. O’Brien CJ. Valente C. Chem. Eur. J. 2007, 13: 150

9 Organ MG. Abdel-Hadi M. Avola S. Dubovyk I. Hadei N. Kantchev EAB. O’Brien CJ. Valente C. Chem. Eur. J. 2008, 14: 2443

10 Wanzlick H.-W. Schönherr H.-J. Angew. Chem., Int. Ed. Engl. 1968, 7: 141

11 Öfele K. J. Organomet. Chem. 1968, 12: P42

12 Arduengo AJ. Harlow RL. Kline M. J. Am. Chem. Soc. 1991, 113: 361

13 Nair V. Bindu S. Sreekumar V. Angew. Chem. Int. Ed. 2004, 43: 5130

14 Perry MC. Burgess K. Tetrahedron: Asymmetry 2003, 14: 951

15 Crudden CM. Allen DP. Coord. Chem. Rev. 2004, 248: 2247

16 Nolan SP. Scott NM. Eur. J. Inorg. Chem. 2005, 1815

17 Crabtree RH. J. Organomet. Chem. 2005, 690: 5451

18 Youngs WJ. Garrison JC. Chem. Rev. 2005, 105: 3978

19 Cavallo L. Correa A. Costabile C. Jacobsen H. J. Organomet. Chem. 2005, 690: 5407

20 Herrmann WA. Fischer EJ. Köchter C. Arthus GRJ. Angew. Chem., Int. Ed. Engl. 1995, 107: 2602

21 Herrmann WA. Mihalios D. Öfele K. Kiprof P. Belmedjahed F. Chem. Ber. 1992, 125: 1795

22 Öfele K. Herrmann WA. Mihalios D. Elison M. Herdtweck E. Scherer W. Mink J. J. Organomet. Chem. 1993, 459: 177

23 Herrmann WA. Öfele K. Elison M. Kuhn FE. Roesky PW. J. Organomet. Chem. 1994, 480: C7

24 Littke AF. Fu GC. Angew. Chem. Int. Ed. 2002, 41: 4176

25 Cárdenas DJ. Angew. Chem. Int. Ed. 1999, 38: 3018

26 Netherton MR. Fu GC. Adv. Synth. Catal. 2004, 346: 1525

27 Frisch AC. Beller M. Angew. Chem. Int. Ed. 2005, 44: 674

28 Valentine DHJ. Hillhouse JH. Synthesis 2003, 2437

29 Dias PB. Piedade MEM. Simões JAM. Coord. Chem. Rev. 1994, 135-136: 737

30 Tolman CA. Chem. Rev. 1977, 77: 313

31 Mauger CC. Mignani GA. Aldrichimica Acta 2006, 39: 17

32 Amyes TL. Diver ST. Richard JP. Rivas FM. Toth K. J. Am. Chem. Soc. 2004, 126: 4366

33 Frohlich N. Pindun U. Stahl M. Frenking G. Organometallics 1997, 16: 442

34 Chen H. Justes DR. Cooks RG. Org. Lett. 2005, 7: 3949

35 Cowley AH. J. Organomet. Chem. 2001, 617-618: 105

36 Chianese AR. Li X. Janzen MC. Faller JW. Crabtree RH. Organometallics 2003, 22: 1663

37 Dorta R. Stevens ED. Scott NM. Costabile C. Cavallo L. Hoff CD. Nolan SP. J. Am. Chem. Soc. 2004, 127: 2485

38 Herrmann WA. Schütz J. Frey GD. Herdtweck E. Organometallics 2006, 25: 2437

39 O’Brien CJ. Kantchev EAB. Chass GA. Hadei N. Hopkinson AC. Organ MG. Setiadi DH. Tang T.-H. Fang D.-C. Tetrahedron 2005, 61: 9723

40 Culkin DA. Hartwig JF. Organometallics 2004, 23: 3398

41 Mann G. Shelby Q. Roy AH. Hartwig JF. Organometallics 2003, 22: 2775

42 Page PCB. Buckley BR. Christie SDR. Edgar M. Poulton AM. Elsegood MRJ. McKee VJ. J. Organomet. Chem. 2005, 690: 6210

43 Lebel H. Janes MK. Charette AB. Nolan SP. J. Am. Chem. Soc. 2004, 126: 5046

44 Ma Y. Song C. Jiang W. Xue G. Cannon JF. Wang X. Andrus MB. Org. Lett. 2003, 5: 4635

45 Love JA. Morgan JP. Trnka TM. Grubbs RG. Angew. Chem. Int. Ed. 2002, 41: 4035

46 Hall DG. Boronic Acids: Preparation Applications in Organic Synthesis and Medicine Wiley-VCH; Weinheim: 2005.

47 Thomas SE. Organic synthesis: the roles of boron and silicon Oxford University Press; Oxford: 1991.

48 de Meijere A. Diederich F. Metal-catalyzed cross-coupling reactions 2nd ed.: Miyarua N. Wiley-VCH; Weinheim: 2004. p.41-123

49 Chemler SR. Trauner D. Danishefsky SJ. Angew. Chem. Int. Ed. 2001, 40: 4544

50 Negishi E.-i. Aspects of Mechanism and Organometallic Chemistry Brewster JH. Plenum; New York: 1978. p.285

51 Negishi E.-i. J. Organomet. Chem. 2002, 653: 34

52 Miyaura N. Yamada K. Suzuki A. Tetrahedron Lett. 1979, 20: 3437

53 Miyarua N. Suzuki A. J. Chem. Soc. Chem. Commun. 1979, 866

54 Bellina F. Carpita A. Rossie R. Synthesis 2004, 2419

55 Miura M. Angew. Chem. Int. Ed. 2004, 43: 2201

56 Miyaura N. Top. Curr. Chem. 2002, 219: 11

57 Suzuki A. J. Organomet. Chem. 1999, 576: 147

58 Miyaura N. Suzuki A. Chem. Rev. 1995, 95: 2457

59 Herrmann WA. Reisinger C.-P. Spiegler M. J. Organomet. Chem. 1998, 557: 93

60 Zhang C. Huang J. Trudell ML. Nolan SP. J. Org. Chem. 1999, 64: 3804

61 Andrus MB. Song C. Org. Lett. 2001, 3: 3761

62 Gstöttmayr CWK. Böhm VPW. Herdtweck E. Grosche M. Herrmann WA. Angew. Chem. Int. Ed. 2002, 41: 1363

63 Altenhoff G. Goddard R. Lehmann CW. Glorius F. Angew. Chem. Int. Ed. 2003, 42: 3690

64 Navarro O. Kelly RA. Nolan SP. J. Am. Chem. Soc. 2003, 125: 16194

65 Song C. Ma Y. Chai Q. Ma C. Jiang W. Andrus MB. Tetrahedron 2005, 61: 7438

66 Altenhoff G. Goddard R. Lehmann CW. Glorius F. J. Am. Chem. Soc. 2004, 126: 15195

67 Navarro O. Kaur H. Mahjoor P. Nolan SP. J. Org. Chem. 2004, 69: 3173

68 Cesar V. Bellemin-Laponnaz S. Gade LH. Organometallics 2002, 21: 5204

69 Palencia H. Garcia-Jimenez F. Takacs JM. Tetrahedron Lett. 2004, 45: 3849

70 Schneider SK. Herrmann WA. Herdtweck E. J. Mol. Catal. 2006, 245: 248

71 Fuller AA. Hester HR. Salo EV. Stevens EP. Tetrahedron Lett. 2003, 44: 2935

72 Abraham MH. Grellier PL. The Chemistry of the Metal-Carbon Bond Hartley FR. Patai S. Wiley; New York: 1985. p.25

73 McDougal NT. Schaus SE. J. Am. Chem. Soc. 2003, 125: 12094

74 McDougal NT. Trevellini WL. Rodgen SA. Kliman LT. Schaus SE. Adv. Synth. Catal. 2004, 346: 1231

75 Perkins JR. Carter RG. J. Am. Chem. Soc. 2008, 130: 3290

76 Littke AF. Dai C. Fu GC. J. Am. Chem. Soc. 2000, 122: 4020

77 Barder TE. Walker SD. Martinelli JR. Buchwald SL. J. Am. Chem. Soc. 2005, 127: 4749

78 Arentsen K. Caddick S. Cloke FGN. Herring AP. Hitchcock PB. Tetrahedron Lett. 2004, 45: 3511

79 Singh R. Viciu MS. Kramareva N. Navarro O. Nolan SP. Org. Lett. 2005, 7: 1829

80 Tamao K. Sumitani K. Kumada M. J. Am. Chem. Soc. 1972, 94: 4374

81 Corriu RJP. Masse JP. Chem. Commun. 1972, 144

82 Yamamura M. Moritani I. Murahashi S. J. Organomet. Chem. 1975, 61: C39

83 Huang J. Nolan SP. J. Am. Chem. Soc. 1999, 121: 9889

84 Frisch AC. Rataboul F. Zapf A. Beller M. J. Organomet. Chem. 2003, 687: 403

85 Frisch AC. Zapf A. Briel O. Kayser B. Shaikh N. Beller M. J. Mol. Catal. 2004, 214: 231

86 Negishi E.-i. King AO. Okukado N. J. Org. Chem. 1977, 42: 1821

87 King AO. Okukado N. Negishi E.-i. Chem. Commun. 1977, 683

88 Knochel P. Jones P. Organozinc Reagents - A Practical Approach Oxford University Press; Oxford: 1999.

89 Iyer S. Jayanthi A. Synlett 2003, 1125

90 Zhou J. Fu GC. J. Am. Chem. Soc. 2003, 125: 12527

91 Zhu L. Wehmeyer RM. Rieke RD. J. Org. Chem. 1991, 56: 1445

92 Rieke RD. Hanson MV. Brown JD. Niu QJ. J. Org. Chem. 1996, 61: 2726

93 Hadei N. Kantchev EAB. O’Brien CJ. Organ MG. Org. Lett. 2005, 7: 3805

94 Hou S. Org. Lett. 2003, 5: 423

95 Kosugi M. Kameyama M. Migita T. Chem. Lett. 1983, 927

96 Boger DL. Panek JS. Tetrahedron Lett. 1984, 25: 3175

97 Kondratenko NV. Kolomeitsev AA. Mogilevskaya VO. Varlamova NM. Yagupol’skii LM. J. Org. Chem. USSR (Engl. Transl.) 1986, 22: 1547 ; translated from Zh. Org. Khim. 1986, 22, 1721 (original article submitted March 26, 1985)

98 Guram AS. Rennels RA. Buchwald SL. Angew. Chem. Int. Ed. 1995, 34: 1348

99 Louie J. Hartwig JF. Tetrahedron Lett. 1995, 36: 3609

100 Schlummer B. Scholz U. Adv. Synth. Catal. 2004, 346: 1599

101 Muci AR. Buchwald SL. Top. Curr. Chem. 2002, 219: 131

102 Huang J. Grasa GA. Nolan SP. Org. Lett. 1999, 1: 1307

103 Grasa GA. Viciu MS. Huang J. Nolan SP. J. Org. Chem. 2001, 66: 7729

104 Viciu MS. Germaneau RF. Navarro O. Stevens ED. Nolan SP. Organometallics 2002, 21: 5470

105 Viciu MS. Kissling RM. Stevens ED. Nolan SP. Org. Lett. 2002, 4: 2229

106 Viciu MS. Kelly RA. Stevens ED. Naud F. Studer M. Nolan SP. Org. Lett. 2003, 5: 1479

107 Navarro O. Marion N. Scott NM. González J. Amoroso D. Bell A. Nolan SP. Tetrahedron 2005, 61: 9716

108 Marion N. Navarro O. Mei J. Stevens ED. Scott NM. Nolan SP. J. Am. Chem. Soc. 2006, 128: 4101

109 Navarro O. Marion N. Mei J. Nolan SP. Chem. Eur. J. 2006, 12: 5142

110 Stauffer SR. Hartwig JF. J. Am. Chem. Soc. 2003, 125: 6977

111 Titcomb LR. Caddick S. Cloke FGN. Wilson DJ. McKerrecher D. Chem. Commun. 2001, 1388

112 Organ MG. Comer E. Chem. Eur. J. 2005, 11: 7223

113 Comer E. Organ MG. J. Am. Chem. Soc. 2005, 127: 8160

114 Shore G. Morin S. Mallik D. Organ MG. Chem. Eur. J. 2008, 14: 1351

115 Barluenga J. Fernandez MA. Aznar F. Valdes C. Chem. Eur. J. 2005, 11: 2276

116 Lerma IC. Cawley MJ. Arentsen K. Scott JS. Pearlson SE. Hayler J. Caddick S. J. Organomet. Chem. 2005, 690: 5841

117 Ananikov VP. Musaev DG. Morokuma KJ. J. Am. Chem. Soc. 2002, 124: 2839

118 Ananikov VP. Musaev DG. Morokuma KJ. Organometallics 2005, 24: 715

119 Chin W. Mons M. Dognon J.-P. Mirasol R. Chass G. Dimicoli I. Piuzzi F. Butz P. Tardivel B. Compagnon I. von Helden G. Meijer G. J. Phys. Chem. A 2005, 109: 5281

120 Chass GA. Mirasol RS. Setiadi DH. Tang T.-H. Chin W. Mons M. Dimicoli I. Dognon J.-P. Viskolcz B. Lovas S. Penke B. Csizmadia IG. J. Phys. Chem. A 2005, 109: 5289

121 Chass GA. Marai CNJ. Harrison AG. Csizmadia KJ. J. Phys. Chem. A 2002, 106: 9695

122 Richardson TB. de Gala S. Crabtree RH. Siegbahn PEM. J. Am. Chem. Soc. 1995, 117: 12875

123 Robertson KN. Knop O. Cameron TS. Can. J. Chem. 2003, 81: 727

124 Alkorta M. Elguero J. Grabowski SJ. J. Phys. Chem. A 2008, 112: 2721

125 Frisch MJ. Trucks GW. Schlegel HB. Scuseria GE. Robb MA. Cheeseman JR. Montgomery JA. Vreven JT. Kudin KN. Burant JC. Millam JM. Iyengar SS. Tomasi J. Barone V. Mennucci B. Cossi M. Scalmani G. Rega N. Petersson GA. Nakatsuji H. Hada MEM. Toyota K. Fukuda R. Hasegawa J. Ishida M. Nakajima T. Honda Y. Kitao O. Nakai H. Klene M. Li X. Knox JE. Hratchian HP. Cross JB. Adamo C. Jaramillo J. Gomperts R. Stratmann RE. Yazyev O. Austin AJ. Cammi R. Pomelli C. Ochterski JW. Ayala PY. Morokuma K. Voth GA. Salvador P. Dannenberg JJ. Zakrzewski VG. Dapprich S. Daniels AD. Strain MC. Farkas O. Malick DK. Rabuck AD. Raghavachari K. Foresman JB. Ortiz JV. Cui Q. Baboul AG. Clifford S. Cioslowski J. Stefanov BB. Liu G. Liashenko A. Piskorz P. Komaromi I. Martin RL. Fox DJ. Keith T. Al-Laham MA. Peng CY. Nanayakkara A. Challacombe M. Gill PMW. Johnson B. Chen W. Wong MW. Gonzalez C. Pople JA. Gaussian 03, revision B.02 Gaussian, Inc.; Pittsburgh (PA): 2003.

126 Godbout N. Salahub DR. Andzelm J. Wimmer E. Can. J. Chem. 1992, 70: 560

127 Becke AD. J. Chem. Phys. 1993, 98: 5648

128 Lee C. Yang W. Parr RG. Phys. Rev. B. 1988, 37: 785

129 Miertus S. Scrocco E. Tomasi J. Chem. Phys. 1981, 55: 117

130 Barone V. Cossi M. Tomasi J. J. Chem. Phys. 1997, 107: 3210

131 Barone V. Cossi M. J. Phys. Chem. A. 1998, 120: 1995

132 Mucsi Z. Szabó A. Hermecz I. Kucsman Á. Csizmadia IG. J. Am. Chem. Soc. 2005, 127: 7615

133 Wulf ORUL. Hendericks SB. J. Am. Chem. Soc. 1936, 58: 2287

134 Tamres M. J. Am. Chem. Soc. 1952, 74: 3375

135 Burkley SK. Petsko GA. Adv. Protein Chem. 1988, 39: 125

136 Steiner T. Acta Crystallogr., Sect. D 1998, 54: 584

137 Steiner T. Koellner G. J. Mol. Biol. 2001, 305: 535

138 Duan G. Smith VH. Weaver DF. Chem. Phys. Lett. 1999, 310: 323

139 Duan G. Smith VH. Weaver DF. Int. J. Quantum Chem. 2000, 80: 44

140 Bader RFW. Acc. Chem. Res. 1985, 18: 9

141 Bader RFW. Atoms in Molecules, A Quantum Theory Clarendon Press; Oxford UK: 1990.

142 Matta CF. Hernandez-Trujillo J. Tang T.-H. Bader RFW. Chem. Eur. J. 2003, 9: 1940

143 Popelier PLA. J. Phys. Chem. A 1998, 102: 1873

144 Bader RFW. Fang D.-C. J. Chem. Theory Comput. 2005, 1: 403

145 Platts JA. Howard ST. Bracke BRF. J. Am. Chem. Soc. 1996, 118: 2726

146 Platts JA. Howard ST. J. Chem. Phys. 1996, 105: 4668

147 Koch U. Popelier PLA. J. Phys. Chem. 1995, 99: 9747

148 Gatti C. Saunders VR. Roetti C. J. Chem. Phys. 1994, 101: 10686

149 Espinosa E. Molins E. Lecomte C. Chem. Phys. Lett. 1998, 285: 170

150 Espinosa E. Souhassou M. Lachekar H. Lecomte C. Acta Crystallogr., Sect. B 1999, 55: 563

151 Rendeif EE. Dahaoui S. Renali-Cherif N. Lecomte C. Acta Crystallogr., Sect. B 2007, 63: 448

152 Albert S. Pillet S. Lecomte C. Pradel A. Ribes M. Acta Crystallogr., Sect. B 2008, 64: 1

153 Aubert E. Lecomte C. J. Appl. Crystallogr. 2007, 40: 1153

154 Koritsansky TS. Coppens P. Chem. Rev. 2001, 101: 1583

155 Flaig R. Koritsanszky TS. Dittrich B. Wagner A. Luger P. J. Am. Chem. Soc. 2002, 124: 3407

156 Lee C.-R. Tang T.-H. Chen L. Wang Y. Chem. Eur. J. 2003, 9: 3112

157 Guillot B. Jelsch C. Podjarny A. Lecomte C. Acta Crystallogr., Sect. D 2008, 64: 567

158 Tang T.-H. Deretey E. Knak Jensen SJ. Csizmadia IG. Eur. Phys. J., D: Atom Mol. Opt. Phys. 2006, 37: 217

159 Cortes-Guzman F. Richard RFW. Coord. Chem. Rev. 2005, 249: 633