Harnessing the Versatile Reactivity of Propargyl Alcohols and their Derivatives for Sustainable Complex Molecule Synthesis

Abstract

One of the major challenges faced in modern synthetic chemistry is the efficient and selective assembly of complex molecular structures, especially carbo- and heterocycles, from readily accessible starting materials. With this has arisen the development of tandem reaction processes, which permit multiple transformations in a single synthetic step and that have often provided elegant routes to complex target scaffolds from simple precursors. Propargyl alcohols and their derivatives have become increasingly attractive starting materials for such processes owing to their reactivity in the presence of a Brønsted or Lewis acid catalyst as well as halogenation reagents. This account describes our recent efforts in the field, and demonstrates how propargyl alcohols and their derivatives can be transformed into a diverse range of highly functionalized acyclic, carbocyclic and heterocyclic structures, which are of importance as synthetic building blocks and as motifs in functional materials and bioactive compounds.

1 Introduction

2 Acyclic Conjugated Enynes

3 Carbocycles

3.1 Indenes

3.2 Dihydrofluorenes

3.3 Cyclopentenes, Cyclobutenes and Cyclopenta[b]naphthalenes

3.4 ortho-Phenolic Esters

4 Heterocycles with One Heteroatom

4.1 Indoles

4.2 Piperidines, Azepines and Pyrrolidines

4.3 Pyrroles

4.4 Furans

4.5 Benzo[b]oxepines and Benzo[b]azepines

5 Heterocycles with Two Heteroatoms

5.1 Thiazoles and Oxazoles

5.2 Dioxolanes

6 Conclusion

Key words

alkynes - carbocycles - heterocycles - homogeneous catalysis - tandem reactions

• References


For selected reviews of tandem synthetic processes, see:
• 1a Domino Reactions . Tietze LF. Wiley-VCH; Weinheim: 2014
• 1b Behr A, Vorholt AJ, Ostrowski KA, Seidensticker T. Green Chem. 2014; 16: 982
• 1c Pellìssier H. Tetrahedron 2013; 69: 7171
• 1d Fustero S, Sanchez-Rosello M, del Pozo C. Pure Appl. Chem. 2010; 82: 669
• 1e Moores A In Handbook of Green Chemistry . Anastas PT, Crabtree RH. Wiley-VCH; Weinheim: 2009: 1
• 1f Nicolaou KC, Edmonds DJ, Bulger PG. Angew. Chem. Int. Ed. 2006; 45: 7134
• 1g Hall N. Science 1994; 266: 32

For selected reviews concerning the reactivity of unsaturated substrates and transition metal complexes, see:
• 2a Yamamoto Y. Chem. Soc. Rev. 2014; 43: 1575
• 2b Gulevich AV, Dudnik AS, Chernyak N, Gevorgyan V. Chem. Rev. 2013; 113: 3084
• 2c Zhu Z.-B, Kirsch SF. Chem. Commun. 2013; 49: 2272
• 2d Barreiro EM, Adrio LA, Hii KK, Brazier JB. Eur. J. Org. Chem. 2013; 1027
• 2e Patil NT, Kavthe RD, Shinde VS. Tetrahedron 2012; 68: 8079
• 2f Shu X.-Z, Shu D, Schienebeck CM, Tang W. Chem. Soc. Rev. 2012; 41: 7698
• 2g Marinetti A, Jullien H, Voituriez A. Chem. Soc. Rev. 2012; 41: 4884
• 2h Fehr C. Synlett 2012; 23: 990
• 2i Leyva-Pérez A, Corma A. Angew. Chem. Int. Ed. 2012; 51: 614
• 2j Aubert C, Fensterbank L, Garcia P, Malacria M, Simonneau A. Chem. Rev. 2011; 111: 1954
• 2k Hao L, Zhan Z.-P. Curr. Org. Chem. 2011; 15: 1625
• 2l Nishizawa M, Imagawa H, Yamamoto H. Org. Biomol. Chem. 2010; 8: 511
• 2m Michelet V, Toullec PY, Genêt J.-P. Angew. Chem. Int. Ed. 2008; 47: 4268
• 2n Patil NT, Yamamoto Y. Chem. Rev. 2008; 108: 3395
• 2o Yamamoto Y. J. Org. Chem. 2007; 72: 7817
• 2p Fürstner A, Davies PW. Angew. Chem. Int. Ed. 2007; 46: 3410
• 2q Michelet V, Charrault L, Gladiali S, Genêt J.-P. Pure Appl. Chem. 2006; 78: 397
• 2r Modern Allene Chemistry . Krause N, Hashmi AS. K. Wiley-VCH; Weinheim: 2005

For selected reviews concerning the reactions of propargyl alcohols and derivatives in the presence of gold catalysts, see refs 2e,f,i,k,m,n,p, and:
• 3a Acc. Chem. Res. 2014; 47: 729 ; an issue dedicated to gold catalysis
• 3b Gold Catalysis: An Homogeneous Approach . Toste FD, Michelet V. Imperial College Press; London: 2014
• 3c Shiroodi RK, Gevorgyan V. Chem. Soc. Rev. 2013; 42: 4991
• 3d Rudolph M, Hashmi AS. K. Chem. Soc. Rev. 2012; 41: 2448
• 3e Modern Gold Catalyzed Synthesis . Hashmi AS. K, Toste FD. Wiley-VCH; Weinheim: 2012
• 3f Garayalde D, Nevado C. ACS Catal. 2012; 2: 1462
• 3g Alcaide B, Almendros P, Alonso JM. Org. Biomol. Chem. 2011; 9: 4405
• 3h Krause N, Winter C. Chem. Rev. 2011; 111: 1994
• 3i Corma A, Leyva-Perez A, Sabater MJ. Chem. Rev. 2011; 111: 1657
• 3j Wang S, Zhang G, Zhang L. Synlett 2010; 692
• 3k Fürstner A. Chem. Soc. Rev. 2009; 38: 3208
• 3l Marion N, Nolan SP. Angew. Chem. Int. Ed. 2007; 46: 2750
• 3m Marco-Contelles J, Soriano E. Chem. Eur. J. 2007; 13: 1350
• 3n Gorin DJ, Toste FD. Nature 2007; 446: 395
• 3o Ma S, Yu S, Gu Z. Angew. Chem. Int. Ed. 2006; 45: 200

For selected reviews concerning the reactions of propargyl alcohols and derivatives in the presence of silver catalysts, see refs 2e,k,n,p, and:
• 4a Silver in Organic Chemistry . Hamata M. John Wiley & Sons; Hoboken: 2010
• 4b Álvarez-Corral M, Muñoz-Dorado M, Rodríguez-García I. Chem. Rev. 2008; 108: 3174
• 4c Weibel J.-M, Blanc A, Pale P. Chem. Rev. 2008; 108: 3149

For selected reviews, see:
• 5a Baeza A, Nájera C. Synthesis 2014; 46: 25
• 5b Narelda RR, Klumpp DA. Chem. Rev. 2013; 113: 6905
• 5c Gualandi A, Cozzi PG. Synlett 2013; 24: 281
• 5d Cera G, Chiarucci M, Bandini M. Pure Appl. Chem. 2012; 84: 1673
• 5e Bauer EB. Synthesis 2012; 44: 1131
• 5f Bandini M, Cera G, Chiarucci M. Synthesis 2012; 44: 504
• 5g Biannic B, Aponick A. Eur. J. Org. Chem. 2011; 6605
• 5h Emer E, Sinisi R, Capdevila MG, Petruzziello D, De Vincentiis F, Cozzi PG. Eur. J. Org. Chem. 2011; 647
• 5i Rueping M, Nachtsheim BJ. Beilstein J. Org. Chem. 2010; 6: No. 6
• 5j Bandini M, Tragni M. Org. Biomol. Chem. 2009; 7: 1501
• 5k Muzart J. Tetrahedron 2008; 64: 5815
• 5l Muzart J. Tetrahedron 2005; 61: 9423
• 5m Lewis Acids in Organic Synthesis . Yamamoto H. Wiley-VCH; Weinheim: 2000
• 6 Rao W, Zhang X, Sze EM. L, Chan PW. H. J. Org. Chem. 2009; 74: 1740
• 7 Mothe SR, Chan PW. H. J. Org. Chem. 2009; 74: 5887
• 8a Yamauchi Y, Onodera G, Sakata K, Yuki M, Miyake Y, Uemura S, Nishibayashi Y. J. Am. Chem. Soc. 2007; 129: 5175
• 8b Xiao H.-Q, Shu X.-Z, Ji K.-G, Qi C.-Z, Liang Y.-M. New J. Chem. 2007; 31: 2041

For selected reviews, see:
• 9a El-Shazly M, Barve BD, Korinek M, Liou J.-R, Chuang D.-W, Cheng Y.-B, Hou M.-F, Wang J.-J, Wu Y.-C, Chang F.-R. Curr. Top. Med. Chem. 2014; 14: 1076
• 9b Shirtcliff LD, McClintock SP, Haley MM. Chem. Soc. Rev. 2008; 37: 343
• 9c Doucet H, Hierso J.-C. Angew. Chem. Int. Ed. 2007; 46: 834
• 9d Zeni G, Braga AL, Stefani HA. Acc. Chem. Res. 2003; 36: 731
• 10 Zhang X, Teo WT, Chan PW. H. Org. Lett. 2009; 11: 4990

For recent selected examples concerning indene synthesis, see:
• 11a Muthusamy S, Sivaguru M. Org. Lett. 2014; 16: 4248
• 11b Rosocha G, Batey RA. Tetrahedron 2013; 69: 8758
• 11c Liu L, Fan Y, He Q, Zhang Y, Zhang-Negrerie D, Huang J, Du Y, Zhao K. J. Org. Chem. 2012; 77: 3997
• 11d Panteleev J, Huang RY, Lui EK. J, Lautens M. Org. Lett. 2011; 13: 5314
• 11e Akagawa K, Sakamoto S, Kudo K. Synlett 2011; 817
• 11f Reddy BV. S, Reddy BB, Rao KV. R, Yadav JS. Tetrahedron Lett. 2010; 51: 5697
• 11g Liu C.-R, Yang F.-L, Jin Y.-Z, Ma X.-T, Cheng D.-J, Li N, Tian S.-K. Org. Lett. 2010; 12: 3832
• 11h Yamazaki S, Yamamoto Y, Fukushima Y, Takebayashi M, Ukai T, Mikata Y. J. Org. Chem. 2010; 75: 5216
• 12 Rao W, Chan PW. H. Org. Biomol. Chem. 2010; 8: 4016
• 13a Maraval V, Duhayon C, Coppel Y, Chauvin R. Eur. J. Org. Chem. 2008; 5144
• 13b Feng A.-H, Chen J.-Y, Yang L.-M, Lee G.-H, Wang Y, Luh T.-Y. J. Org. Chem. 2001; 66: 7922

For selected examples, see:
• 14a Zhu H.-T, Ji K.-G, Yang F, Wang L.-J, Zhao S.-C, Ali S, Liu S, Liang X.-Y, Liang Y.-M. Org. Lett. 2011; 13: 684
• 14b Smith CD, Rosocha G, Mui L, Batey RA. J. Org. Chem. 2010; 75: 4716
• 14c Zhou X, Zhang H, Xie X, Li Y. J. Org. Chem. 2008; 73: 3958
• 14d Guo S, Liu Y. Org. Biomol. Chem. 2008; 6: 2064
• 14e Xi Z, Guo R, Mito S, Yan H, Kanno K.-I, Nakajima K, Takahashi T. J. Org. Chem. 2003; 68: 1252
• 15 Zhang X, Teo WT, Rao W, Ma D.-L, Leung C.-H, Chan PW. H. Tetrahedron Lett. 2014; 55: 3881

For selected examples of gold-catalyzed 1,n-enyne ester migrations, see:
• 16a Yu Y, Yang W, Rominger F, Hashmi AS. K. Angew. Chem. Int. Ed. 2013; 52: 7586
• 16b Rao W, , Sally Koh MJ, Chan PW. H. J. Org. Chem. 2013; 78: 3183
• 16c Hashmi AS. K, Yang W, Yu Y, Hansmann MM, Rudolph M, Rominger F. Angew. Chem. Int. Ed. 2013; 52: 1329
• 16d Rao W, Susanti D, Chan PW. H. J. Am. Chem. Soc. 2011; 133: 15248
• 16e Garayalde D, Gómez-Bengoa E, Huang X, Goeke A, Nevado C. J. Am. Chem. Soc. 2010; 132: 4720
• 16f Mauleón PJ, Krinsky L, Toste FD. J. Am. Chem. Soc. 2009; 131: 4513
• 16g Uemura M, Watson ID. G, Katsukawa M, Toste FD. J. Am. Chem. Soc. 2009; 131: 3464
• 16h Lemiére G, Gandon V, Cariou K, Hours A, Fukuyama T, Dhimane A.-L, Fensterbank L, Malacria M. J. Am. Chem. Soc. 2009; 131: 2993
• 16i Watson ID. G, Ritter S, Toste FD. J. Am. Chem. Soc. 2009; 131: 2056
• 16j Zou Y, Garayalde D, Wang Q, Nevado C, Goeke A. Angew. Chem. Int. Ed. 2008; 47: 10110
• 16k Boyer F.-D, Le Goff X, Hanna I. J. Org. Chem. 2008; 73: 5163
• 16l Li G, Zhang G, Zhang L. J. Am. Chem. Soc. 2008; 130: 3740
• 16m Moreau X, Goddard J.-P, Bernard M, Lemière G, López-Romero JM, Mainetti E, Marion N, Mouriès V, Thorimbert S, Fensterbank L, Malacria M. Adv. Synth. Catal. 2008; 350: 43
• 16n Lemiére G, Gandon V, Cariou K, Fukuyama T, Dhimane A.-L, Fensterbank L, Malacria M. Org. Lett. 2007; 9: 2207
• 16o Buzas A, Gagosz F. J. Am. Chem. Soc. 2006; 128: 12614
• 16p Marion N, de Frémont P, Stevens ED, Fensterbank L, Malacria M, Nolan SP. Chem. Commun. 2006; 2048
• 16q Buzas A, Istrate F, Gagosz F. Org. Lett. 2006; 8: 1957
• 16r Zhang L, Wang S. J. Am. Chem. Soc. 2006; 128: 1442
• 16s Zhang L. J. Am. Chem. Soc. 2005; 127: 16804
• 16t Mamane V, Gress T, Krause H, Fürstner A. J. Am. Chem. Soc. 2004; 126: 8654

For selected examples of gold-catalyzed 1,n-diyne ester migrations, see:
• 17a Li D, Rao W, Tay GL, Ayers BJ, Chan PW. H. J. Org. Chem. 2014; 79: 11301
• 17b Rao W, Chan PW. H. Chem. Eur. J. 2014; 20: 713
• 17c Oh CH, Kim JH, Piao L, Yu J, Kim SY. Chem. Eur. J. 2013; 19: 10501
• 17d Rao W, Koh MJ, Li D, Hirao H, Chan PW. H. J. Am. Chem. Soc. 2013; 135: 7926
• 17e Lauterbach T, Gatzweiler S, Nösel P, Rudolph M, Rominger F, Hashmi AS. K. Adv. Synth. Catal. 2013; 355: 2481
• 17f Rao W, Koh MJ, Kothandaraman P, Chan PW. H. J. Am. Chem. Soc. 2012; 134: 10811
• 17g Leboeuf D, Simonneau A, Aubert C, Malacria M, Gandon V, Fensterbank L. Angew. Chem. Int. Ed. 2011; 50: 6868
• 17h Zhang D.-H, Yao L.-F, Wei Y, Shi M. Angew. Chem. Int. Ed. 2011; 50: 2583
• 17i Luo T, Schreiber SL. J. Am. Chem. Soc. 2009; 131: 5667
• 17j Oh CH, Kim A. Synlett 2008; 777
• 17k Luo T, Schreiber SL. Angew. Chem. Int. Ed. 2007; 46: 8250
• 17l Oh CH, Kim A. New J. Chem. 2007; 31: 1719
• 17m Zhao J, Hughes CO, Toste FD. J. Am. Chem. Soc. 2006; 128: 7436
• 17n Oh CH, Kim A, Park W, Park DI, Kim N. Synlett 2006; 2781

For recent selected examples concerning dihydrofluorene synthesis, see:
• 18a Hashmi AS. K, Hoffmann J, Shi S, Schütz A, Rudolph M, Lothschütz C, Wieteck M, Bührle M, Wölfle M, Rominger F. Chem. Eur. J. 2013; 19: 382
• 18b Garcia-Garcia P, Rashid MA, Sanjuan AM, Fernandez-Rodriguez MA, Sanz R. Org. Lett. 2012; 14: 4778
• 18c Zhang L, Xie X, Liu J, Qi J, Ma D, She X. Org. Lett. 2011; 13: 2956
• 18d Chaudhuri R, Liao H.-YM, Liu RS. Chem. Eur. J. 2009; 15: 8895
• 18e Gorin J, Watson ID. G, Toste FD. J. Am. Chem. Soc. 2008; 130: 3736
• 18f Liu W, Buck M, Chen N, Shang M, Taylor NJ, Asoud J, Wu X, Hasinoff BB, Dmitrienko GI. Org. Lett. 2007; 9: 2915

To our knowledge, only two prior reports have been described, see:
• 19a Briones JF, Davies HM. L. J. Am. Chem. Soc. 2012; 134: 11916
• 19b Witham CA, Mauleón P, Shapiro ND, Sherry BD, Toste FD. J. Am. Chem. Soc. 2007; 129: 5838
• 20 For illustrative examples of dual activation in gold catalysis, see: Braun I, Asiri AM, Hashmi AS. K. ACS Catal. 2013; 3: 1902 ; and references cited therein

For recent selected examples concerning cyclopenta[b]naphthalenes, see:
• 21a Wang X.-C, Hu J, Sun P.-S, Zhong M.-J, Ali S, Liang Y.-M. Org. Biomol. Chem. 2011; 9: 7461
• 21b Kotha S, Halder S. Synlett 2010; 337
• 21c Ahn JH, Shin MS, Jung SH, Kim JA, Kim HM, Kim SH, Kang SK, Kim KR, Rhee SD, Park SD, Lee JM, Lee JH, Cheon HG, Kim SS. Bioorg. Med. Chem. Lett. 2007; 17: 5239
• 21d Scaglione JB, Manion BD, Benz A, Taylor A, DeKoster GT, Rath NP, Evers AS, Zorumski CF, Mennerick S, Covey DF. J. Med. Chem. 2006; 49: 4595
• 21e Kim KR, Lee JH, Kim SJ, Rhee SD, Jung WH, Yang S.-D, Kim SS, Ahn JH, Cheon HG. Biochem. Pharmacol. 2006; 72: 446

For recent selected examples concerning bicyclo[3.2.0]hepta-1,5-dienes, see:
• 22a Xin X, Wang D, Wu F, Wang C, Wang H, Li X, Wan B. Org. Lett. 2013; 15: 4512
• 22b Tam W, Jack K, Goodreid J, Cockburn N. Adv. Org. Synth. 2013; 6: 59
• 22c Dembitsky VM. J. Nat. Med. 2008; 62: 1
• 22d Oh CH, Gupta AK, Park DI, Kim N. Chem. Commun. 2005; 5670
• 23 For examples of 1,5-acyl migrations in gold catalysis, see refs 16b, 17f, and 17g.
• 24 Teo WT, Rao W, Ng CJ. H, Koh SW. Y, Chan PW. H. Org. Lett. 2014; 16: 1248
• 25a Butler MS. Nat. Prod. Rep. 2008; 25: 475
• 25b Yet L. Chem. Rev. 2003; 103: 4283
• 25c Rappoport Z. The Chemistry of Phenols . Wiley-VCH; Weinheim: 2003
• 25d Phenol Derivatives in Ullmann's Encyclopedia of Industrial Chemistry . Fiegel H, Voges HW, Hamamoto T, Umemura S, Iwata T, Miki H, Fujita Y, Buysch HJ, Garbe D, Paulus W. Wiley-VCH; New York: 2002
• 25e Höller U, König GM, Wright AD. J. Nat. Prod. 1999; 62: 114
• 25f Synthetic and Natural Phenols . Tyman JH. P. Elsevier; New York: 1996

For recent selected examples, see:
• 26a Liu W, Ackermann L. Org. Lett. 2013; 15: 3484
• 26b Shen Y, Liu G, Zhou Z, Lu X. Org. Lett. 2013; 15: 3366
• 26c Shan G, Han X, Lin Y, Yu S, Rao Y. Org. Biomol. Chem. 2013; 11: 2318
• 26d Yang F, Ackermann L. Org. Lett. 2013; 15: 718
• 26e Lee D.-H, Kwon K.-H, Yi CS. J. Am. Chem. Soc. 2012; 134: 7325
• 26f Thirunavukkarasu VS, Ackermann L. Org. Lett. 2012; 14: 6206
• 26g Thirunavukkarasu VS, Hubrich J, Ackermann L. Org. Lett. 2012; 14: 4210
• 26h Yang Y, Lin Y, Rao Y. Org. Lett. 2012; 14: 2874
• 27 Persich P, Llaveria J, Lhermet R, de Haro T, Stade R, Kondoh A, Fürstner A. Chem. Eur. J. 2013; 19: 13047

For selected reviews, see:
• 28a Shiri M. Chem. Rev. 2012; 112: 3508
• 28b Barluenga J, Valdes C In Modern Heterocyclic Chemistry . Alvarez-Builla J, Vaquero JJ, Barluenga J. Wiley-VCH; Weinheim: 2011
• 28c Vicente R. Org. Biomol. Chem. 2011; 9: 6469
• 28d Palmisano G, Penoni A, Sisti M, Tibiletti F, Tollari S, Nicholas KM. Curr. Org. Chem. 2010; 14: 2409
• 28e Sharma V, Kumar P, Pathak D. J. Heterocycl. Chem. 2010; 47: 491
• 28f Barluenga J, Rodriguez F, Fananas FJ. Chem. Asian J. 2009; 4: 1036
• 28g Miyata O, Takeda N, Naito T. Heterocycles 2009; 78: 843

For recent selected examples concerning indoles, see:
• 29a Li H, Li X, Wang H.-Y, Winston-McPherson GN, Geng H.-MJ, Guzei IA, Tang W. Chem. Commun. 2014; 50: 12293
• 29b Saito T, Sonoki Y, Otani T, Kutsumura N. Org. Biomol. Chem. 2014; 12: 8398
• 29c Winston-McPherson GN, Shu D, Tang W. Bioorg. Med. Chem. Lett. 2014; 24: 4023
• 29d Ren L, Shi Z, Jiao N. Tetrahedron 2013; 69: 4408
• 29e Shu D, Winston-McPherson GN, Song W, Tang W. Org. Lett. 2013; 15: 4162
• 29f Lee Y.-T, Jang Y.-J, Syu S.-E, Chou S.-C, Lee C.-J, Lin W. Chem. Commun. 2012; 48: 8135
• 29g Hashmi AS. K, Yang W, Rominger F. Chem. Eur. J. 2012; 18: 6576
• 30 Kothandaraman P, Rao W, Foo SJ, Chan PW. H. Angew. Chem. Int. Ed. 2010; 49: 4619
• 31 Susanti D, Koh F, Kusuma JA, Kothandaraman P, Chan PW. H. J. Org. Chem. 2012; 77: 7166

For illustrative examples, see:
• 32a Yang F, Jin T, Bao M, Yamamoto Y. Tetrahedron 2011; 67: 10147
• 32b Ravindar K, Reddy MS, Deslongchamps P. Org. Lett. 2011; 13: 3178
• 32c Ji K.-G, Zhu H.-T, Yang F, Shaukat A, Xia X.-F, Yang Y.-F, Liu X.-Y, Liang Y.-M. J. Org. Chem. 2010; 75: 5670
• 32d Zhang X, Lu Z, Fu C, Ma S. J. Org. Chem. 2010; 75: 2589
• 32e Aponick A, Li C.-Y, Malinge J, Marques EF. Org. Lett. 2009; 11: 4624
• 33 Mothe SR, Kothandaraman P, Lauw SJ. L, Chin SM. W, Chan PW. H. Chem. Eur. J. 2012; 18: 6133

For selected recent examples, see:
• 34a Tolnai GL, Ganss S, Brand JP, Waser J. Org. Lett. 2013; 15: 112
• 34b Danilkina NA, Bräse S, Balova IA. Synlett 2011; 517
• 34c Yang L, Zhao L, Li C.-J. Chem. Commun. 2010; 46: 4184
• 34d Berciano BP, Lebrequier S, Besselièvre F, Piguel S. Org. Lett. 2010; 12: 4038
• 34e Dudnik AS, Gevorgyan V. Angew. Chem. Int. Ed. 2010; 49: 2096
• 34f Kim SH, Chang S. Org. Lett. 2010; 12: 1868
• 34g Kawano T, Matsuyama N, Hirano K, Satoh T, Miura M. J. Org. Chem. 2010; 75: 1764
• 34h Besselièvre F, Piguel S. Angew. Chem. Int. Ed. 2009; 48: 9553
• 34i Brand JP, Charpentier J, Waser J. Angew. Chem. Int. Ed. 2009; 48: 9346
• 34j Matsuyama N, Hirano K, Satoh T, Miura M. Org. Lett. 2009; 11: 4156
• 34k Tobisu M, Ano Y, Chatani N. Org. Lett. 2009; 11: 3250
• 34l Gu Y, Wang XM. Tetrahedron Lett. 2009; 50: 763
• 34m Seregin IV, Ryabova V, Gevorgyan V. J. Am. Chem. Soc. 2007; 129: 7742
• 34n Nagamochi M, Fang Y.-Q, Lautens M. Org. Lett. 2007; 9: 2955
• 35 Mothe SR, Novianti ML, Ayers BJ, Chan PW. H. Org. Lett. 2014; 16: 4110

See ref. 16q, and:
• 36a Weyrauch JP, Hashmi AS. K, Schuster A, Hengst T, Schetter S, Littmann A, Rudolph M, Hamzic M, Visus J, Rominger F, Frey W, Bats JW. Chem. Eur. J. 2010; 16: 956
• 36b Yu M, Zhang G, Zhang L. Org. Lett. 2007; 9: 2147
• 36c Kirsch SF, Binder JT, Crone B, Duschek A, Haug TT, Liébert C, Menz H. Angew. Chem. Int. Ed. 2007; 46: 2310
• 36d Buzas A, Gagosz F. Synlett 2006; 2727
• 37 For a review comparing gold catalysis with iodonium activation of alkynes, see: Hummel S, Kirsch SF. Beilstein J. Org. Chem. 2011; 7: 847
• 38 Kothandaraman R, Mothe SR, Toh SS. M, Chan PW. H. J. Org. Chem. 2011; 76: 7633
• 39 Kothandaraman P, Koh BQ, Limpanuparb T, Hirao H, Chan PW. H. Chem. Eur. J. 2013; 19: 1978

For recent selected reviews on 2- and 3-oxindole synthesis, see:
• 40a Dalpozzo R, Bartoli G, Bencivenni G. Chem. Soc. Rev. 2012; 41: 7247
• 40b Singh GS, Desta ZY. Chem. Rev. 2012; 112: 6104
• 40c Shen K, Liu X, Lin L, Feng X. Chem. Sci. 2012; 3: 327
• 40d Klein JE. M. N, Taylor RJ. K. Eur. J. Org. Chem. 2011; 6821
• 40e Trost BM, Brennan MK. Synthesis 2009; 3003

For selected reviews on haloamination of unsaturated bonds, see:
• 41a Parvatkar PT, Parameswaran PS, Tilve SG. Chem. Eur. J. 2012; 18: 5460
• 41b Godoi B, Schumacher RF, Zeni G. Chem. Rev. 2011; 111: 2937
• 41c Yamamoto Y, Gridnev ID, Patil NT, Jin T. Chem. Commun. 2009; 5075
• 41d Mphahlele MJ. Molecules 2009; 14: 4814
• 41e Stavber S, Jereb M, Zupan M. Synthesis 2008; 1487
• 41f Togo H, Iida S. Synlett 2006; 2159
• 41g Larock RC In Acetylene Chemistry: Chemistry, Biology, and Material Science . Diederich F, Stang PJ, Tykwinski RR. Wiley-VCH; New York: 2005: 51
• 42a Ali S, Zhu H.-T, Xia X.-F, Ji K.-G, Yang Y.-F, Song X.-R, Liang Y.-M. Org. Lett. 2011; 13: 2598
• 42b Hessian KO, Flynn BL. Org. Lett. 2006; 8: 243
• 43 Kothandaraman P, Lauw SJ. L, Chan PW. H. Tetrahedron 2013; 69: 7471
• 44 Ohta Y, Chiba H, Oishi S, Fujii N, Ohno H. J. Org. Chem. 2009; 74: 7052
• 45 Susanti D, Ng LL. R, Chan PW. H. Adv. Synth. Catal. 2014; 356: 353

For selected examples concerning azabicyclo[4.2.0]oct-5-enes, see:
• 46a Kashiwada Y, Yamazaki K, Ikeshiro Y, Yamagashi T, Fujioka T, Mihashi K, Mizuki K, Cosentino LM, Fowke K, Morris-Natschke SL, Lee K.-H. Tetrahedron 2001; 57: 1559
• 46b Kurata K, Taniguchi K, Agatsuma Y, Suzuki M. Phytochemistry 1998; 47: 363
• 46c Crimmins MT, Huang S, Guise-Zawacki LE. Tetrahedron Lett. 1996; 37: 6519
• 46d Piers E, Lu Y.-F. J. Org. Chem. 1989; 54: 2267

For selected examples concerning azabicyclo[4.2.0]octa-1(8),5-dienes, see:
• 47a Hu J, Tian B, Wu X, Tong X. Org. Lett. 2012; 14: 5074
• 47b Saito N, Tanaka Y, Sato Y. Org. Lett. 2009; 11: 4124
• 47c Mukai C, Hara Y, Miyashita Y, Inagaki F. J. Org. Chem. 2007; 72: 4454
• 48 Wang W, Hammond GB, Xu BJ. J. Am. Chem. Soc. 2012; 134: 5697
• 49 Rao W, , Sally Berry SN, Chan PW. H. Chem. Eur. J. 2014; 20: 13174
• 50 For the only known example of a cycloisomerization of 1,6,8-dienynes into cyclohexa-1,4-dienes under gold catalysis, see: Kim SM, Park JH, Chung YK. Chem. Commun. 2011; 47: 6719
• 51a Yeon H.-S, So E, Shin S. Chem. Eur. J. 2011; 17: 1764
• 51b Nakamura I, Yamagishi U, Song D, Konta S, Yamamoto Y. Chem. Asian J. 2008; 3: 285
• 51c Nakamura I, Yamagishi U, Song D, Konta S, Yamamoto Y. Angew. Chem. Int. Ed. 2007; 46: 2284
• 52 Teo WT, Rao W, Koh MJ, Chan PW. H. J. Org. Chem. 2013; 78: 7508

For recent examples illustrating pyrrole synthesis, see:
• 53a Chang M.-Y, Cheng Y.-C, Lu Y.-J. Org. Lett. 2014; 16: 6252
• 53b Gujarathi S, Liu X, Song L, Hendrickson H, Zheng G. Tetrahedron 2014; 70: 5267
• 53c Yang W, Zhou Y, Sun H, Zhang L, Zhao F, Liu H. RSC Adv. 2014; 68: 1113
• 53d Billedeau RJ, Klein KR, Kaplan D, Lou Y. Org. Lett. 2013; 15: 1421
• 53e Chen F, Shen T, Cui Y, Jiao N. Org. Lett. 2012; 14: 4926
• 53f Thompson BB, Montgomery J. Org. Lett. 2011; 13: 3289
• 53g Aginagalde M, Bello T, Masdeu C, Vara Y, Arrieta A, Cossio Fernando P. J. Org. Chem. 2010; 75: 7435
• 53h Ackermann L, Sandmann R, Kaspar LT. Org. Lett. 2009; 11: 2031
• 53i St Cyr DJ, Arndtsen BA. J. Am. Chem. Soc. 2007; 129: 12366
• 53j Binder JT, Kirsch SF. Org. Lett. 2006; 8: 2151
• 54 Zhang X, Teo JW, Ma D.-L, Leung C.-H, Chan PW. H. ­Tetrahedron Lett. 2014; 55: 6703
• 55 For representative examples, see refs 25c and 32a.
• 56 Aponick A, Li C.-Y, Palmes JA. Org. Lett. 2009; 11: 121

For selected reviews concerning furan motifs, see:
• 57a Lorente A, Lamariano-Merketegi J, Albericio F, Alvarez M. Chem. Rev. 2013; 113: 4567
• 57b Wong HN. C, Hou X.-L, Yeung K.-S, Huang H In Modern Heterocyclic Chemistry . Alvarez-Builla J, Vaquero JJ, Barluenga J. Wiley-VCH; Weinheim: 2011: 533
• 57c Boto A, Alvarez L In Heterocycles in Natural Product Synthesis . Majumdar KC, Chattopadhyay SK. Wiley-VCH; Weinheim: 2010: 99
• 57d Senning A In Comprehensive Heterocyclic Chemistry III . Katritzky AR, Rees CW, Scriven EF. V, Taylor RJ. K. Pergamon; New York: 2008: 389
• 57e The Chemistry of Heterocycles: Structures, Reactions, Synthesis, and Applications. Eicher T, Hauptmann S. Wiley-VCH; Weinheim: 2003
• 57f Wright DL. Chem. Innov. 2001; 31: 17

For selected examples illustrating furan synthesis, see:
• 58a Palisse A, Kirsch SF. Eur. J. Org. Chem. 2014; 7095
• 58b Yue Y, Zhang Y, Song W, Zhang X, Liu J, Zhou K. Adv. Synth. Catal. 2014; 356: 2459
• 58c Chen Z.-W, Luo M.-T, Wen Y.-L, Zhou Z.-G, Liu L.-X. Synlett 2014; 25: 2341
• 58d Hoffmann M, Miaskiewicz S, Weibel J.-M, Pale P, Blanc A. Beilstein J. Org. Chem. 2013; 9: 1774
• 58e Cao H, Zhan H, Cen J, Lin Y, Zhu Q, Fu M, Jiang H. Org. Lett. 2013; 15: 1080
• 58f Li E, Cheng X, Wang C, Shao Y, Li Y. J. Org. Chem. 2012; 77: 7744
• 58g Umland K.-D, Palisse A, Haug TT, Kirsch SF. Angew. Chem. Int. Ed. 2011; 50: 9965
• 58h Li W, Zhang J. Chem. Commun. 2010; 46: 8839
• 58i Cao H, Jiang H, Yao W, Liu X. Org. Lett. 2009; 11: 1931
• 58j Feng X, Tan Z, Chen D, Shen Y, Guo C.-C, Xiang J, Zhu C. Tetrahedron Lett. 2008; 49: 4110
• 58k Jung HH, Floreancig PE. J. Org. Chem. 2007; 72: 7359
• 58l Suhre MH, Reif M, Kirsch SF. Org. Lett. 2005; 7: 3925
• 59 Mothe SR, Lauw SJ. L, Kothandaraman P, Chan PW. H. J. Org. Chem. 2012; 77: 6937

For selected examples, see:
• 60a Kashima K, Sano K, Yun YS, Ina H, Kunugi A, Inoue H. Chem. Pharm. Bull. 2010; 58: 191
• 60b Kim S, Su B.-N, Riswan S, Kardono LB. S, Afriastini JJ, Gallucci JC, Chai H, Farnsworth NR, Cordell GA, Swanson SM, Kinghorn AD. Tetrahedron Lett. 2005; 46: 9021
• 60c Engler M, Anke T, Sterner OJ. J. Antibiot. 1997; 50: 330
• 60d Engler M, Anke T, Sterner OJ, Brandt UJ. J. Antibiot. 1997; 50: 325
• 60e Macías FA, Molinillo JM. G, Varela RM, Torres A, Fronczek FR. J. Org. Chem. 1994; 59: 8261
• 60f Asakawa Y, Hashimoto T, Takikawa K, Tori M, Ogawa S. Phytochemistry 1991; 30: 235

For recent selected examples, see:
• 61a Bera K, Jalal S, Sarkar S, Jana U. Org. Biomol. Chem. 2014; 12: 57
• 61b Rohlmann R, Daniliuc C.-G, Mancheno OG. Chem. Commun. 2013; 49: 11665
• 61c Choi YL, Lim HS, Lim HJ, Heo J.-N. Org. Lett. 2012; 14: 5102
• 61d Liu J, Liu Y. Org. Lett. 2012; 14: 4742
• 61e Varela-Fernandéz A, Garcia-Yebra C, Varela JA, Esteruelas MA, Saa C. Angew. Chem. Int. Ed. 2010; 49: 4278
• 61f Majumdar KC, Sinha B, Ansary I, Chakraborty S. Synlett 2010; 1407
• 62 Sze EM. L, Rao W, Koh MJ, Chan PW. H. Chem. Eur. J. 2011; 17: 1437

For selected examples, see:
• 63a Yea CM, Allan CE, Ashworth DM, Barnett J, Baxter AJ, Broadbridge JD, Franklin RJ, Hampton SL, Hudson P, Horton JA, Jenkins PD, Penson AM, Pitt GR. W, Rivière P, Robson PA, Rooker DP, Semple G, Sheppard A, Haigh RM, Roe MB. J. Med. Chem. 2008; 51: 8124
• 63b Xiang MA, Rybczynski PJ, Patel M, Chen RH, McComsey DF, Zhang H.-C, Gunnet JW, Look R, Wang Y, Minor LK, Zhong HM, Villani FJ, Demarest KT, Damianob BP, Maryanoff BE. Bioorg. Med. Chem. Lett. 2007; 17: 6623
• 63c Nakamura S, Yamamura Y, Itoh S, Hirano T, Tsujimae K, Aoyama M, Kondo K, Ogawa H, Shinohara T, Kan K, Tanada Y, Teramoto S, Sumida T, Nakayama S, Sekiguchi K, Kambe T, Tsujimoto G, Mori T, Tominaga M. Br. J. Pharmacol. 2000; 129: 1700
• 63d Yamamura Y, Nakamura S, Ito S, Hirano T, Onogawa T, Yamashita T, Yamada Y, Tsujimae K, Aoyama M, Kotosai K, Ogawa H, Yamashita H, Kondo K, Tominaga M, Tsujimoto G, Mori T. J. Pharmacol. Exp. Ther. 1998; 287: 860

For recent selected examples, see:
• 64a Jalal S, Bera K, Sarkar S, Paul K, Jana U. Org. Biomol. Chem. 2014; 12: 1759
• 64b Benedetti E, Lornazzi M, Tibiletti F, Goddard J.-P, Fensterbank L, Malacria M, Palmisano G, Penoni A. Synthesis 2012; 44: 3523
• 64c Wang L, Huang J, Peng S, Liu H, Jiang X, Wang J. Angew. Chem. Int. Ed. 2013; 53: 1768
• 64d Kothandaraman P, Huang C, Susanti D, Rao W, Chan PW. H. Chem. Eur. J. 2011; 17: 10081
• 64e He H, Liu W.-B, Dai L.-X, You S.-L. Angew. Chem. Int. Ed. 2010; 49: 1496
• 64f González-Gómez Á, Domínguez G, Pérez-Castells J. Eur. J. Org. Chem. 2009; 5057
• 65 Sze EL. M, Koh MJ, Tjia YM, Rao W, Chan PW. H. Tetrahedron 2013; 69: 5558

For selected reviews, see:
• 66a Just-Baringo X, Albericio F, Alvarez M. Curr. Top. Med. Chem. 2014; 14: 1244
• 66b Jin Z. Nat. Prod. Rep. 2013; 30: 869
• 66c Heterocyclic Chemistry in Drug Discovery . Li JJ. John Wiley & Sons; Hoboken: 2013
• 66d Walsh CT, Malcolmson SJ, Young TS. ACS Chem. Biol. 2012; 7: 429
• 66e Tomer I, Mishra R, , Priyanka Sharma NK, Jha KK. J. Pharm. Res. 2011; 4: 2975
• 66f Turner CD, Liang HS. Curr. Org. Chem. 2011; 15: 2846
• 66g Revuelta J, Machetti F, Cicchi S In Modern Heterocyclic Chemistry . Alvarez-Builla J, Vaquero JJ, Barluenga J. Wiley-VCH; Weinheim: 2011: 809
• 66h Davyt D, Serra G. Mar. Drugs 2010; 8: 2755
• 67a Gao X, Pan Y.-M, Lin M, Chen L, Zhan Z.-P. Org. Biomol. Chem. 2010; 8: 3259
• 67b Yoshimatsu M, Yamamoto T, Sawa A, Kato T, Tanabe G, Muraoka O. Org. Lett. 2009; 11: 2952
• 68 Zhang X, Teo WT, , Sally Chan PW. H. J. Org. Chem. 2010; 75: 6290
• 69a Kumar MP, Liu R.-S. J. Org. Chem. 2006; 71: 4951
• 69b Milton MD, Inada Y, Nishibayashi Y, Uemura S. Chem. Commun. 2004; 2712
• 70 Zhang X, Teo WT, Chan PW. H. J. Organomet. Chem. 2011; 696: 331
• 71 Pan Y.-M, Zheng F.-J, Lin H.-X, Zhan Z.-P. J. Org. Chem. 2009; 74: 3148
• 72a Huple DB, Liu R.-S. Chem. Commun. 2012; 48: 10975
• 72b Molawi K, Delpont N, Echavarren AM. Angew. Chem. Int. Ed. 2010; 49: 3517
• 72c Schelweis M, Moser R, Dempwolff AL, Rominger F, Helmchen G. Chem. Eur. J. 2009; 15: 10888
• 72d Escribano-Cuesta A, López-Carrillo V, Janssen D, Echavarren AM. Chem. Eur. J. 2009; 15: 5646
• 72e Shelweis M, Dempwolff AL, Rominger F, Helmchen G. Angew. Chem. Int. Ed. 2007; 46: 5598
• 72f Jiménez-Núnez E, Claverie CK, Nieto-Oberhuber C, Echavarren AM. Angew. Chem. Int. Ed. 2006; 45: 5452