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Synlett 2010(5): 675-691  
DOI: 10.1055/s-0029-1219369
ACCOUNT
© Georg Thieme Verlag Stuttgart ˙ New York

A Reactivity-Driven Approach to the Discovery and Development of Gold-Catalyzed Organic Reactions

Nathan D. Shapiro, F. Dean Toste*
Department of Chemistry, University of California, Berkeley, California 94720, USA
Fax: +1(510)6662504; e-Mail: fdtoste@berkeley.edu;
Further Information

Publication History

Received 17 December 2009
Publication Date:
08 February 2010 (online)

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Abstract

Approaches to research in organic chemistry are as numerous as the reactions they describe. In this account, we describe our reactivity-based approach. Using our work in the area of gold catalysis as a background, we discuss how a focus on reaction mechanism and reactivity paradigms can lead to the rapid discovery of new synthetic tools.

1 Introduction

2 Addition Reactions

2.1 Conia-Ene Reaction

2.2 Asymmetric Hydroamination

2.3 Chiral Counteranions

2.4 Exploiting Basic Counteranions

2.5 Ring Expansion Reactions

2.6 Intramolecular Carboalkoxylation

2.7 Rationalizing the π-Acidity of Cationic Gold(I) Complexes

3 Reactions Involving Carbenoid Intermediates

3.1 1,5-Enyne Cycloisomerization

3.2 Intramolecular Addition of Dipolar Nucleophiles to Alkynes

3.3 Stereospecific Cyclopropanation

3.4 Gold-Carbon Bonding in Cationic Intermediates and Relativistic Effects

3.5 A Bonding Model for Gold(I)-Carbene Complexes

4 Further Insights into Reactivity from Gold-Catalyzed ­Cycloisomerization Reactions

4.1 Intramolecular Rearrangements of 1,5-Enynes

4.2 Ligand- and Substrate-Controlled Access to [2+2], [3+2], [4+2], and [4+3] Cycloadditions in Gold-Catalyzed Reactions of Allene-Enes

5 Intermolecular Annulation Reactions

5.1 A [4+3] Annulation Approach to Azepines

5.2 Orbital Considerations in [3+3] Annulations

6 Tandem Reactions

7 Conclusions

Key words

gold catalysis - enantioselective catalysis - cycloisomerizations - alkynes - allenes

    References

  • 1 Lewis GN. Science  1909,  30:  1 
    CrossrefGoogle Scholar
  • For more-recent discussions relevant to this approach, see:
  • 2a Nicolaou KC. Snyder SA. Proc. Natl. Acad. Sci. U.S.A.  2004,  101:  11929 
    Google Scholar
  • 2b Mohr JT. Krout MR. Stoltz BM. Nature  2008,  455:  323 
    Google Scholar
  • 2c Shenvi RA. O’Malley DP. Baran PS. Acc. Chem. Res.  2009,  42:  530 
    Google Scholar
  • 2d Wender PA. Verma VA. Paxton TJ. Pillow TH. Acc. Chem. Res.  2008,  41:  40 
    Google Scholar
  • 2e Young IS. Baran PS. Nat. Chem.  2009,  1:  193 
    Google Scholar
  • 2f Morten CJ. Byers JA. Van Dyke AR. Vilotijevic I. Jamison TF. Chem. Soc. Rev.  2009,  38:  3175 
    Google Scholar
  • 3a Grubbs RH. Chang S. Tetrahedron  1998,  54:  4413 
    Google Scholar
  • 3b Dick AR. Sanford MS. Tetrahedron  2006,  62:  2439 
    Google Scholar
  • 3c Hartwig JF. Nature  2008,  455:  314 
    Google Scholar
  • 3d Buchwald SL. Acc. Chem. Res.  2008,  41:  1439 
    Google Scholar
  • 3e Sherry BD. Fürstner A. Acc. Chem. Res.  2008,  41:  1500 
    Google Scholar
  • 3f Fu GC. Acc. Chem. Res.  2008,  41:  1555 
    Google Scholar
  • 3g Afagh NA. Yudin AK. Angew. Chem. Int. Ed.  2010,  49:  262 
    Google Scholar
  • 4a Francis MB. Jamison TF. Jacobsen EN. Curr. Opin. Chem. Biol.  1998,  2:  422 
    Google Scholar
  • 4b Weber L. Illgen K. Almstetter M. Synlett  1999,  366 
    Google Scholar
  • 4c Kanan MW. Rozenman MM. Sakurai K. Snyder TM. Liu DR. Nature  2004,  431:  545 
    Google Scholar
  • 4d Beeler AB. Su S. Singleton CA. Porco JA. J. Am. Chem. Soc.  2007,  129:  1413 
    Google Scholar
  • 4e Rozenman MM. Kanan MW. Liu DR. J. Am. Chem. Soc.  2007,  129:  14933 
    Google Scholar
  • 4f Gorin DJ. Kamlet AS. Liu DR. J. Am. Chem. Soc.  2009,  131:  9189 
    Google Scholar
  • For selected examples that highlight this approach, see:
  • 5a Sharpless KB. Angew. Chem. Int. Ed.  2002,  41:  2024 
    Google Scholar
  • 5b Johnson JS. Evans DA. Acc. Chem. Res.  2000,  33:  325 
    Google Scholar
  • 5c Fu GC. Acc. Chem. Res.  2000,  33:  412 
    Google Scholar
  • 5d Fulton JR. Holland AW. Fox DJ. Bergman RG. Acc. Chem. Res.  2002,  35:  44 
    Google Scholar
  • 5e Trost BM. Acc. Chem. Res.  2002,  35:  695 
    Google Scholar
  • 5f Saito S. Yamamoto H. Acc. Chem. Res.  2004,  37:  570 
    Google Scholar
  • 5g Enders D. Neimeier O. Henseler A. Chem. Rev.  2007,  107:  5606 
    Google Scholar
  • 5h MacMillan DWC. Nature  2008,  455:  304 
    Google Scholar
  • 5i Doyle AG. Jacobsen EN. Chem. Rev.  2007,  107:  5713 
    Google Scholar
  • 6 Teles JH. Brode S. Chabanas M. Angew. Chem. Int. Ed.  1998,  37:  1415 
    Google Scholar
  • 7 Nesmeyanov AN. Grandberg KI. Dyadchenko VP. Lemenovskii DA. Perevalova EG. Izv. Akad. Nauk SSSR, Ser. Khim.  1974,  1206 
    Google Scholar
  • 8 Kennedy-Smith JJ. Staben ST. Toste FD. J. Am. Chem. Soc.  2004,  126:  4526 
    Google Scholar
  • 9 The thermally promoted Conia-ene reaction typically proceeds at temperatures above 200 ˚C; for a review, see: Conia JM. Le Perchec P. Synthesis  1975,  1 
    Article in Thieme ConnectGoogle Scholar
  • Additional metal-promoted Conia-ene reactions; Pd-catalyzed:
  • 10a Balme G. Bouyssi D. Faure R. Gore J. Van Hemelryck B. Tetrahedron  1992,  48:  3891 
    Google Scholar
  • Mo-catalyzed:
  • 10b McDonald FE. Olson TC. Tetrahedron Lett.  1997,  38:  7691 
    Google Scholar
  • Cu-catalyzed:
  • 10c Bouyssi D. Monteiro N. Balme G. Tetrahedron Lett.  1999,  40:  1297 
    Google Scholar
  • Ti-mediated:
  • 10d Kitagawa O. Suzuki T. Inoue T. Watanabe Y. Taguchi T. J. Org. Chem.  1998,  63:  9470 
    Google Scholar
  • Hg/H+-catalyzed
  • 10e Boaventura MA. Drouin J. Conia JM. Synthesis  1983,  801 
    Google Scholar
  • Co/hν-catalyzed
  • 10f Renaud J.-L. Aubert C. Malacria M. Tetrahedron  1999,  55:  5113 
    Google Scholar
  • Ni-catalyzed
  • 10g Gao Q. Zheng B.-F. Li J.-H. Yang D. Org. Lett.  2005,  7:  2185 
    Google Scholar
  • Re-catalyzed
  • 10h Kuninobu Y. Kawata A. Takai K. Org. Lett.  2005,  7:  4823 
    Google Scholar
  • 11 A 5-endo-dig variant of this reaction is also viable, see: Staben ST. Kennedy-Smith JJ. Toste FD. Angew. Chem. Int. Ed.  2005,  43:  5350 
    CrossrefGoogle Scholar
  • 12 For a similar study, see: Hashmi ASK. Weyrauch JP. Frey W. Bats JW. Org. Lett.  2004,  6:  4391 
    Google Scholar
  • 13a Akana JA. Bhattacharyya KX. Müller P. Sadighi JP. J. Am. Chem. Soc.  2007,  129:  7736 
    Google Scholar
  • 13b Liu L.-P. Xu B. Mashuta MS. Hammond GB. J. Am. Chem. Soc.  2008,  130:  17642 
    Google Scholar
  • 13c Hashmi ASK. Schuster AM. Rominger F. Angew. Chem. Int. Ed.  2009,  48:  8247 
    Google Scholar
  • 14 We hypothesize that the Brønsted acid suppresses alkyne dimerization, while the Lewis acid increases the enolic character of the keto ester, see also: Trost BM. Sorum MT. Chan C. Harms AE. Rühter G. J. Am. Chem. Soc.  1997,  119:  698 
    CrossrefGoogle Scholar
  • 15a Staben ST. Kennedy-Smith JJ. Huang D. Corkey BK. LaLonde RL. Toste FD. Angew. Chem. Int. Ed.  2006,  45:  5991 
    Google Scholar
  • 15b Corkey BK. Toste FD. J. Am. Chem. Soc.  2007,  129:  2764 
    Google Scholar
  • 16 Linghu X. Kennedy-Smith JJ. Toste FD. Angew. Chem. Int. Ed.  2007,  46:  7671 
    CrossrefGoogle Scholar
  • For reviews of enantioselective hydroamination, see:
  • 17a Hultzsch KC. Org. Biomol. Chem.  2005,  3:  1819 
    Google Scholar
  • 17b Hultzsch KC. Adv. Synth. Catal.  2005,  347:  367 
    Google Scholar
  • 18 LaLonde RL. Sherry BD. Kang EJ. Toste FD. J. Am. Chem. Soc.  2007,  129:  2452 
    CrossrefGoogle Scholar
  • 19 Hamilton GL. Kang EJ. Miriam M. Toste FD. Science  2007,  317:  496 
    CrossrefPubMedGoogle Scholar
  • 20 For another study on the gold(I)-catalyzed asymmetric hydroalkoxylation of allenes, see: Zhang Z. Widenhoefer RA. Angew. Chem. Int. Ed.  2007,  46:  283 
    CrossrefGoogle Scholar
  • 21 LaLonde RL. Wang ZJ. Mba M. Lackner AD. Toste FD. Angew. Chem. Int. Ed.  2010,  49:  598 
    CrossrefGoogle Scholar
  • 22 For a review of chiral anion mediated asymmetric chemistry, see: Lacour J. Hebbe-Viton V. Chem. Soc. Rev.  2003,  32:  373 
    CrossrefGoogle Scholar
  • For other metal-catalyzed, chiral anion mediated asymmetric reactions, see:
  • 23a Llewellyn DB. Adamson D. Arndtsen BA. Org. Lett.  2000,  2:  4165 
    Google Scholar
  • 23b Llewellyn DB. Arndtsen BA. Tetrahedron: Asymmetry  2005,  16:  1789 
    Google Scholar
  • 23c Dorta R. Shimon L. Milstein D. J. Organomet. Chem.  2004,  689:  751 
    Google Scholar
  • 23d Mukherjee S. List B. J. Am. Chem. Soc.  2007,  129:  11336 
    Google Scholar
  • 23e Hu W.-H. Xu X.-F. Zhou J. Liu W.-J. Huang H.-X. Hu J. Yang L.-P. Gong L.-Z. J. Am. Chem. Soc.  2008,  130:  7782 
    Google Scholar
  • 23f Li C. Wang C. Villa-Marcos B. Xiao J. J. Am. Chem. Soc.  2008,  130:  14450 
    Google Scholar
  • 23g Li C. Villa-Marcos B. Xiao J. J. Am. Chem. Soc.  2009,  131:  6967 
    Google Scholar
  • 23h Lu Y. Johnstone TC. Arndtsen BA. J. Am. Chem. Soc.  2009,  131:  11284 
    Google Scholar
  • 24 Ito Y. Sawamura M. Hayashi T. J. Am. Chem. Soc.  1986,  108:  6405 
    Google Scholar
  • 25 Melhado AD. Luparia M. Toste FD. J. Am. Chem. Soc.  2007,  129:  12638 
    CrossrefGoogle Scholar
  • 26 For a racemic, silver-catalyzed variant of this reaction, see: Peddibhotla S. Tepe J. J. Am. Chem. Soc.  2004,  126:  12776 
    CrossrefGoogle Scholar
  • 27 Müller TE. Beller M. Chem. Rev.  1998,  98:  675 
    Google Scholar
  • 28 Markham JP. Staben ST. Toste FD. J. Am. Chem. Soc.  2005,  127:  9708 
    Google Scholar
  • 29 For a review of ligand effects in gold catalysis, see: Gorin DJ. Sherry BD. Toste FD. Chem. Rev.  2008,  108:  3351 
    CrossrefPubMedGoogle Scholar
  • 30 Theoretical calculations support this mechanism, see: Sordo TL. Ardura D. Eur. J. Org. Chem.  2008,  3004 
    CrossrefGoogle Scholar
  • 31 For a review of 1,2-alkyl migrations catalyzed by π-acids, see: Crone B. Kirsch SF. Chem. Eur. J.  2008,  14:  3514 
    CrossrefPubMedGoogle Scholar
  • 32 Sethofer SG. Staben ST. Hung OY. Toste FD. Org. Lett.  2008,  10:  4315 
    Google Scholar
  • 33 Kleinbeck F. Toste FD. J. Am. Chem. Soc.  2009,  131:  9178 
    CrossrefGoogle Scholar
  • For other reports of catalytic asymmetric ring expansions, see:
  • 34a Trost BM. Yasukata T. J. Am. Chem. Soc.  2001,  123:  7162 
    Google Scholar
  • 34b Trost BM. Xie J. J. Am. Chem. Soc.  2006,  128:  6044 
    Google Scholar
  • 34c Trost BM. Xie J. Maulide N. J. Am. Chem. Soc.  2008,  130:  17258 
    Google Scholar
  • 35 Markownikoff W. Justus Liebigs Ann. Chem.  1870,  153:  228 
    Google Scholar
  • For related reactions, see:
  • 36a Cacchi S. Fabrizi G. Pace P. J. Org. Chem.  1998,  63:  1001 
    Google Scholar
  • 36b Fürstner A. Szillat H. Stelzer F. J. Am. Chem. Soc.  2000,  122:  6785 
    Google Scholar
  • 36c Shimada T. Nakamura I. Yamamoto Y. J. Am. Chem. Soc.  2004,  126:  10546 
    Google Scholar
  • 36d Nakamura I. Mizushima Y. Yamamoto Y. J. Am. Chem. Soc.  2005,  127:  15022 
    Google Scholar
  • 36e Nakamura I. Sato T. Yamamoto Y. Angew. Chem. Int. Ed.  2006,  45:  4473 
    Google Scholar
  • 36f Istrate FM. Gagosz F. Org. Lett.  2007,  9:  3181 
    Google Scholar
  • 36g Nakamura I. Yamagishi U. Song D. Konta S. Yamamoto Y. Angew. Chem. Int. Ed.  2007,  46:  2284 
    Google Scholar
  • 36h Nakamura I. Sato T. Terada M. Yamamoto Y. Org. Lett.  2007,  9:  4081 
    Google Scholar
  • 36i Nakamura I. Sato T. Terada M. Yamamoto Y. Org. Lett.  2008,  10:  2649 
    Google Scholar
  • 36j Uemura M. Watson IDG. Katsukawa M. Toste FD. J. Am. Chem. Soc.  2009,  131:  3464 
    Google Scholar
  • 37 Dubé P. Toste FD. J. Am. Chem. Soc.  2006,  128:  12062 
    CrossrefPubMedGoogle Scholar
  • 38 For a review of ‘memory of chirality’, see: Zhao H. Hsu DC. Carlier PR. Synthesis  2005,  1 
    Article in Thieme ConnectGoogle Scholar
  • 39 For studies on the silver/copper-catalyzed Conia-ene reaction, see: Deng C.-L. Zou T. Wang Z.-Q. Song R.-J. Li J.-H. J. Org. Chem.  2009,  74:  412 
    Google Scholar
  • 40 Shapiro ND. Toste FD. Proc. Natl. Acad. Sci. U.S.A.  2008,  105:  2779 
    CrossrefGoogle Scholar
  • For other reports of gold-alkyne complexes, see:
  • 41a Schulte P. Behrens U. Chem. Commun.  1998,  1633 
    Google Scholar
  • 41b Flügge S. Anoop A. Goddard R. Thiel W. Fürstner A. Chem. Eur. J.  2009,  15:  8558 
    Google Scholar
  • 41c

    See also ref. 13a. For a review, see:

    Google Scholar
  • 41d Schmidbaur H. Schier A. Organometallics  2010,  29:  2 
    Google Scholar
  • For similar studies, see:
  • 42a Nechaev MS. Rayón VM. Frenking G. J. Phys. Chem. A  2004,  108:  3134 
    Google Scholar
  • 42b Ziegler T. Rauk A. Inorg. Chem.  1979,  18:  1558 
    Google Scholar
  • 42c Hertwig RH. Koch W. Schröder D. Schwarz H. Hrušák J. Schwerdtfeger P. J. Phys. Chem.  1996,  100:  12253 
    Google Scholar
  • 42d Kim CK. Lee KA. Kim CK. Lee B. Lee HW. Chem. Phys. Lett.  2004,  391:  321 
    Google Scholar
  • 42e Tai H.-C. Krossing I. Seth M. Deubel DV. Organometallics  2004,  23:  2343 
    Google Scholar
  • 43 Luzung MR. Toste FD. J. Am. Chem. Soc.  2003,  125:  15760 
    CrossrefGoogle Scholar
  • 44 Luzung MR. Markham JP. Toste FD. J. Am. Chem. Soc.  2004,  126:  10858 
    Google Scholar
  • For related reports, see:
  • 45a Mamane V. Gress T. Krause H. Fürstner A. J. Am. Chem. Soc.  2004,  126:  8654 
    Google Scholar
  • 45b Harrak Y. Blaszykowski C. Bernard M. Cariou K. Mainetti E. Mouriés V. Dhimane A.-L. Fensterbank L. Malacria M. J. Am. Chem. Soc.  2004,  126:  8656 
    Google Scholar
  • 45c Horino Y. Luzung MR. Toste FD. J. Am. Chem. Soc.  2006,  128:  11364 
    Google Scholar
  • For reviews on cycloisomerizations, see:
  • 46a Aubert C. Buisine O. Malacria M. Chem. Rev.  2002,  102:  813 
    Google Scholar
  • 46b Trost BM. Krische MJ. Synlett  1998,  1 
    Google Scholar
  • 46c Ojima I. Tzamarioudaki M. Li Z. Donovan RJ. Chem. Rev.  1996,  96:  635 
    Google Scholar
  • 47 Gorin DJ. Davis NR. Toste FD. J. Am. Chem. Soc.  2005,  127:  11260 
    CrossrefGoogle Scholar
  • 48 Shapiro ND. Toste FD. J. Am. Chem. Soc.  2007,  129:  4160 
    CrossrefPubMedGoogle Scholar
  • For reviews, see:
  • 49a Wee AGH. Curr. Org. Synth.  2006,  3:  499 
    Google Scholar
  • 49b Davies HML. Beckwith REJ. Chem. Rev.  2003,  103:  2861 
    Google Scholar
  • 49c Davies HML. Antoulinakis EG. Org. React.  2001,  57:  1 
    Google Scholar
  • 49d Ye T. McKervey MA. Chem. Rev.  1994,  94:  1091 
    Google Scholar
  • 49e Modern Catalytic Methods for Organic Synthesis with Diazo Compounds   Doyle MP. McKervey MA. Ye T. Wiley; New York: 1998. 
    Google Scholar
  • 49f Metal-Carbenes in Organic Synthesis   Zaragoza-Dorwald F. Wiley-VCH; Weinheim Germany: 1998. 
    Google Scholar
  • For gold-catalyzed reaction of α-diazo esters, see:
  • 50a Fructos MR. Belderrain TR. de Frémont P. Scott NM. Nolan SP. Díaz-Requejo MM. Pérez PJ. Angew. Chem. Int. Ed.  2005,  44:  5284 
    Google Scholar
  • 50b Fructos MR. de Frémont P. Nolan SP. Díaz-Requejo MM. Pérez PJ. Organometallics  2006,  25:  2237 
    Google Scholar
  • 51 Rautenstrauch V. J. Org. Chem.  1984,  49:  950 
    Google Scholar
  • 52 Shi X. Gorin DJ. Toste FD. J. Am. Chem. Soc.  2005,  127:  5802 
    CrossrefGoogle Scholar
  • 53 Faza ON. López CS. Álvarez R. de Lera AR. J. Am. Chem. Soc.  2006,  128:  2434 
    CrossrefGoogle Scholar
  • 54 Closs GL. Moss RA. J. Am. Chem. Soc.  1964,  86:  4042 
    CrossrefGoogle Scholar
  • 55 Skell PS. Woodworth RC. J. Am. Chem. Soc.  1956,  78:  4496 
    CrossrefGoogle Scholar
  • 56 Johansson MJ. Gorin DJ. Staben ST. Toste FD. J. Am. Chem. Soc.  2005,  127:  18002 
    CrossrefGoogle Scholar
  • 57a Miki K. Ohe K. Uemura S. Tetrahedron Lett.  2003,  44:  2019 
    Google Scholar
  • 57b Miki K. Ohe K. Uemura S. J. Org. Chem.  2003,  68:  8505 
    Google Scholar
  • 57c Miki K. Uemura S. Ohe K. Chem. Lett.  2005,  34:  1068 
    Google Scholar
  • For a related, gold(III)-catalyzed intramolecular cyclopropanation, see:
  • 57d Fürstner A. Hannen P. Chem. Commun.  2004,  2546 
    Google Scholar
  • 58 For a review of enantioselective cyclopropanation, see: Lebel H. Marcoux J.-F. Molinaro C. Charette AB. Chem. Rev.  2003,  103:  977 
    CrossrefPubMedGoogle Scholar
  • 59 Watson IDG. Ritter S. Toste FD. J. Am. Chem. Soc.  2009,  131:  2056 
    CrossrefGoogle Scholar
  • 60a Fürstner A. Szillat H. Gabor B. Mynott R. J. Am. Chem. Soc.  1998,  120:  8305 
    Google Scholar
  • 60b Fürstner A. Stelzer F. Szillat H. J. Am. Chem. Soc.  2001,  123:  11863 
    Google Scholar
  • 60c Nieto-Oberhuber C. Muñoz MP. Buñuel E. Nevado C. Cárdenas DJ. Echavarren AM. Angew. Chem. Int. Ed.  2004,  43:  2402 
    Google Scholar
  • 60d Chatani N. Kataoka K. Murai S. Furukawa N. Seki Y. J. Am. Chem. Soc.  1998,  120:  9104 
    Google Scholar
  • 61 Gorin DJ. Toste FD. Nature  2007,  446:  395 
    CrossrefPubMedGoogle Scholar
  • 62 Pitzer KS. Acc. Chem. Res.  1979,  12:  271 
    CrossrefGoogle Scholar
  • 63 Schwerdtfeger P. Boyd PDW. Burrell AK. Robinson WT. Taylor MJ. Inorg. Chem.  1990,  29:  3593 
    CrossrefGoogle Scholar
  • 64 Benitez D. Shapiro ND. Tkatchouk E. Wang Y. Goddard WA. Toste FD. Nat. Chem.  2009,  1:  482 
    CrossrefGoogle Scholar
  • 65 Irikura KK. Goddard WA. J. Am. Chem. Soc.  1994,  116:  8733 
    CrossrefGoogle Scholar
  • 66 Landis CR. Weinhold F. J. Comput. Chem.  2007,  28:  198 
    CrossrefGoogle Scholar
  • This model is highly reminiscent of the double ‘half-bond’ model proposed for rhodium-carbenoid intermediates, see:
  • 67a Snyder JP. Padwa A. Stengel T. Arduengo AJ. Jockisch A. Kim H.-L. J. Am. Chem. Soc.  2001,  123:  11318 
    Google Scholar
  • 67b Costantino G. Rovito R. Macchiarulo A. Pellicciari R. J. Mol. Struct. (Theochem)  2002,  581:  111 
    Google Scholar
  • 68 Horino Y. Yamamoto T. Ueda K. Kuroda S. Toste FD. J. Am. Chem. Soc.  2009,  131:  2809 
    CrossrefGoogle Scholar
  • 69 For a related study, see: Lemière G. Gandon V. Cariou K. Hours A. Fukuyama T. Dhimane A.-L. Fensterbank L. Malacria M. J. Am. Chem. Soc.  2009,  131:  2993 
    CrossrefGoogle Scholar
  • For related, metal-catalyzed sp³ C-H bond insertions, see:
  • 70a Bhunia S. Liu R.-S. J. Am. Chem. Soc.  2008,  130:  16488 
    Google Scholar
  • 70b Lee SJ. Oh CH. Lee JH. Kim JI. Hong CS. Angew. Chem. Int. Ed.  2008,  47:  7505 
    Google Scholar
  • 70c Cui L. Peng Y. Zhang L. J. Am. Chem. Soc.  2009,  131:  8394 
    Google Scholar
  • 70d

    See also ref. 50b

    Google Scholar
  • 71 Jones WD. Acc. Chem. Res.  2003,  36:  140 
    CrossrefGoogle Scholar
  • 72 Lee JH. Toste FD. Angew. Chem. Int. Ed.  2007,  46:  912 
    CrossrefGoogle Scholar
  • For related transformations, see:
  • 73a Zhang L. Wang S. J. Am. Chem. Soc.  2006,  128:  1442 
    Google Scholar
  • 73b Funami H. Kusama H. Iwasawa N. Angew. Chem. Int. Ed.  2007,  46:  909 
    Google Scholar
  • 73c Lemière G. Gandon V. Cariou K. Fukuyama T. Dhimane A.-L. Fensterbank L. Malacria M. Org. Lett.  2007,  9:  2207 
    Google Scholar
  • 74 Luzung MP. Mauleón P. Toste FD. J. Am. Chem. Soc.  2007,  129:  12402 
    CrossrefPubMedGoogle Scholar
  • 75 For a related mechanism, see: Zhang L. J. Am. Chem. Soc.  2005,  127:  16804 
    CrossrefGoogle Scholar
  • 76 Mauleón P. Zeldin RM. González AZ. Toste FD. J. Am. Chem. Soc.  2009,  131:  6348 
    Google Scholar
  • For related studies, see:
  • 77a Trillo B. López F. Montserrat S. Ujaque G. Castedo L. Lledós A. Mascareñas JL. Chem. Eur. J.  2009,  15:  3336 
    Google Scholar
  • 77b Alonso I. Trillo B. López F. Montserrat S. Ujaque G. Castedo L. Lledós A. Mascareñas JL. J. Am. Chem. Soc.  2009,  131:  13020 
    Google Scholar
  • See also:
  • 78a Lemière G. Gandon V. Agenet N. Goddard J.-P. de Kozak A. Aubert C. Fensterbank L. Malacria M. Angew. Chem. Int. Ed.  2006,  45:  7596 
    Google Scholar
  • 78b Gorin DJ. Watson IDG. Toste FD. J. Am. Chem. Soc.  2008,  130:  3736 
    Google Scholar
  • 78c Xia Y. Dudnik AS. Gevorgyan V. Li Y. J. Am. Chem. Soc.  2008,  130:  6940 
    Google Scholar
  • 79 González AZ. Toste FD. Org. Lett.  2010,  12:  200 
    CrossrefGoogle Scholar
  • 80 Benitez D. Tkatchouk E. Gonzalez A. Goddard WA. Toste FD. Org. Lett.  2009,  11:  4798 
    CrossrefGoogle Scholar
  • 81a Amijs CHM. López-Carrillo V. Echavarren AM. Org. Lett.  2007,  9:  4021 
    Google Scholar
  • 81b Leseurre L. Toullec PY. Genêt J.-P. Michelet V. Org. Lett.  2007,  9:  4049 
    Google Scholar
  • 82 Nieto-Oberhuber C. López S. Echavarren AM. J. Am. Chem. Soc.  2005,  127:  6178 
    Google Scholar
  • 83 Witham CA. Mauleón P. Shapiro ND. Sherry BD. Toste FD. J. Am. Chem. Soc.  2007,  129:  5838 
    Google Scholar
  • 84a Nieto-Oberhuber C. Muñoz MP. López S. Jiménez-Núñez E. Nevado C. Herrero-Gómez E. Raducan M. Echavarren AM. Chem. Eur. J.  2006,  12:  1677 
    Google Scholar
  • 84b Nieto-Oberhuber C. López S. Muñoz MP. Jiménez-Núñez E. Bunuel E. Cárdenas DJ. Echavarren AM. Chem. Eur. J.  2006,  12:  1694 
    Google Scholar
  • 84c López S. Herrero-Gómez E. Pérez-Galán P. Nieto-Oberhuber C. Echavarren AM. Angew. Chem. Int. Ed.  2006,  45:  6029 
    Google Scholar
  • For related, gold-catalyzed intermolecular annulations, see:
  • 85a Asao N. Takahashi K. Lee S. Kasahara T. Yamamoto Y. J. Am. Chem. Soc.  2002,  124:  12650 
    Google Scholar
  • 85b Kusama H. Miyashita Y. Takaya J. Iwasawa N. Org. Lett.  2006,  8:  289 
    Google Scholar
  • 85c Zhang G. Huang X. Li G. Zhang L. J. Am. Chem. Soc.  2008,  130:  1814 
    Google Scholar
  • 85d Zhang G. Zhang L. J. Am. Chem. Soc.  2008,  130:  12598 
    Google Scholar
  • 86a Doyle MP. Hu W. Timmons DJ. Org. Lett.  2001,  3:  3741 
    Google Scholar
  • 86b Doyle MP. Yan M. Hu W. Gronenberg LS. J. Am. Chem. Soc.  2003,  125:  4692 
    Google Scholar
  • 86c Davies HML. Hu B. Saikali E. Bruzinski PR. J. Org. Chem.  1994,  59:  4535 
    Google Scholar
  • For related reactions of Fischer carbenes, see:
  • 86d Barluenga J. Tomás M. Ballesteros A. Santamaria J. Carbajo RJ. López-Ortiz F. Garcia-Granda S. Pertierra P. Chem. Eur. J.  1996,  2:  88 
    Google Scholar
  • 86e Barluenga J. Tomás M. Rubio E. López-Pelegrín JA. García-Granda S. Priede MP. J. Am. Chem. Soc.  1999,  121:  3065 
    Google Scholar
  • 87a Hashmi ASK. Weyrauch JP. Rudolph M. Kurpejović E. Angew. Chem. Int. Ed.  2004,  43:  6545 
    Google Scholar
  • 87b Hashmi ASK. Kurpejović E. Wölfle M. Frey W. Bats JW. Adv. Synth. Catal.  2007,  349:  1743 
    Google Scholar
  • 88 Shapiro ND. Toste FD. J. Am. Chem. Soc.  2008,  130:  9244 
    CrossrefPubMedGoogle Scholar
  • 89 Hansch C. Leo A. Taft RW. Chem. Rev.  1991,  91:  165 
    Google Scholar
  • 90a Barluenga J. Rodrígues F. Fañanás FJ. Flórez J. Top. Organomet. Chem.  2004,  13:  59 
    Google Scholar
  • 90b Barluenga J. Santamaría J. Tomás M. Chem. Rev.  2004,  104:  2259 
    Google Scholar
  • 90c Sierra MA. Fernández I. Cossío FP. Chem. Commun.  2008,  4671 
    Google Scholar
  • 91a Carbene Chemistry: From Fleeting Intermediates to Powerful Reagents   Bertrand G. Marcel Dekker; New York: 2002. 
    Google Scholar
  • 91b Moss RA. Platz MS. Jones M. Reactive Intermediate Chemistry   Wiley-Interscience; Hoboken / NJ: 2004. 
    Google Scholar
  • 92 Nucleophilic singlet vinylcarbenes react as three-carbon units in cycloadditions with olefins, see: Boger DL. Wysocki RJ. J. Org. Chem.  1988,  53:  3408 
    CrossrefGoogle Scholar
  • 93a Hoffmann R. Zeiss GD. Van Dine GW. J. Am. Chem. Soc.  1968,  90:  1485 
    Google Scholar
  • 93b Davis JH. Goddard WA. Bergman RG. J. Am. Chem. Soc.  1977,  99:  2427 
    Google Scholar
  • 93c Sevin A. Arnaud-Danon L. J. Org. Chem.  1981,  46:  2346 
    Google Scholar
  • 93d Yoshimine M. Pacansky J. Honjou N. J. Am. Chem. Soc.  1989,  111:  2785 
    Google Scholar
  • 94 Shapiro ND. Shi Y. Toste FD. J. Am. Chem. Soc.  2009,  131:  11654 
    CrossrefPubMedGoogle Scholar
  • 95 Walji AM. MacMillan DWC. Synlett  2007,  1477 
    Article in Thieme ConnectGoogle Scholar
  • 96 Gorin DJ. Dubé P. Toste FD. J. Am. Chem. Soc.  2006,  128:  14480 
    Google Scholar
  • 97a Reetz MT. Sommer K. Eur. J. Org. Chem.  2003,  3485 
    Google Scholar
  • 97b Shi Z. He C. J. Org. Chem.  2004,  69:  3669 
    Google Scholar
  • 97c Tarselli MA. Liu A. Gagne MR. Tetrahedron  2009,  65:  1785 
    Google Scholar
  • 98 Sherry BD. Toste FD. J. Am. Chem. Soc.  2004,  126:  15978 
    CrossrefGoogle Scholar
  • 99 Sherry BD. Maus L. Laforteza BN. Toste FD. J. Am. Chem. Soc.  2006,  128:  8132 
    CrossrefGoogle Scholar
  • 100 Mauleón P. Krinsky JL. Toste FD. J. Am. Chem. Soc.  2009,  131:  4513 
    CrossrefGoogle Scholar