Detour and Direct Induction of Methyl-Containing Chiral Centers via Catalytic C–H or C–C Bond Formation

Abstract

The asymmetric induction of chiral centers bearing a methyl group is a fundamental protocol for the synthesis of valuable molecules in biologically active compounds. However, the direct asymmetric methylation is typically difficult to achieve. The present review describes recent representatives of detour and direct approaches to the construction of methyl-containing chiral centers via catalytic C–H or C–C bond formation.

1 Introduction

2 Detour Approaches

2.1 Enzymatic Transformation

2.2 Hydrogenation (Reduction)

2.3 Hydroboration and Suzuki–Miyaura Cross-Coupling

2.4 Hydroformylation

2.5 Cross-Coupling Reaction

2.6 Conjugate Addition

2.7 S_N2′ Methylation

2.8 α-Alkylation

2.9 C–H Functionalization

2.10 Friedel–Crafts Reaction

2.11 Diels–Alder Reaction

2.12 Miscellaneous

3 Direct Approaches

3.1 Carbometallation

3.2 S_N2′ Methylation

3.3 Conjugate Addition

3.4 Ring-Opening Reaction

3.5 Trifluoromethylation

4 Concluding Remarks

Key words

asymmetric catalysis - asymmetric synthesis - chirality - natural products - methylation

• References

• 1 Review: Hall M, Bommarius AS. Chem. Rev. 2011; 111: 4088
• 2a Friest JA, Maezato Y, Broussy S, Blum P, Berkowitz DB. J. Am. Chem. Soc. 2010; 132: 5930
• 2b Paetzold J, Bäckvall JE. J. Am. Chem. Soc. 2005; 127: 17620
• 3a Mazuela J, Verendel JJ, Coll M, Schäffner B, Börner A, Andersson PG, Pàmies O, Diéguez M. J. Am. Chem. Soc. 2009; 131: 12344
• 3b Mazuela J, Norrby P.-O, Andersson PG, Pámies O, Diéguez M. J. Am. Chem. Soc. 2011; 133: 13634
• 3c Zhao J, Burgess K. J. Am. Chem. Soc. 2009; 131: 13236
• 3d Benhaim C, Bouchard L, Pelletier G, Sellstedt J, Kristofova L, Daigneault S. Org. Lett. 2010; 12: 2008
• 4a Hughes G, Kimura M, Buchwald SL. J. Am. Chem. Soc. 2003; 125: 11253
• 4b Lipshutz BH, Servesko JM, Taft BR. J. Am. Chem. Soc. 2004; 126: 8352
• 5 Jang H.-Y, Hughes FW, Gong H, Zhang J, Brodbelt JS, Krische MJ. J. Am. Chem. Soc. 2005; 127: 6174
• 6 Carroll A.-M, O’Sullivan TP, Guiry PJ. Adv. Synth. Catal. 2005; 347: 609
• 7a Crudden CM, Hleba YB, Chen AC. J. Am. Chem. Soc. 2004; 126: 9200
• 7b Moteki SA, Wu D, Chandra KL, Reddy DS, Takacs JM. Org. Lett. 2006; 8: 3097
• 8 Imao D, Glasspoole BW, Laberge VS, Crudden CM. J. Am. Chem. Soc. 2009; 131: 5024
• 9a Chea H, Sim H.-S, Yun J. Adv. Synth. Catal. 2009; 351: 855
• 9b Sandrock DL, Jean-Gérard L, Chen C.-y, Dreher SD, Molander GA. J. Am. Chem. Soc. 2010; 132: 17108
• 10a Yan Y, Zhang X. J. Am. Chem. Soc. 2006; 128: 7198
• 10b Robert T, Abiri Z, Wassenaar J, Sandee AJ, Romanski S, Neudörfl J.-M, Schmalz H.-G, Reek JN. H. Organometallics 2010; 29: 478
• 10c McDonald RI, Wong GW, Neupane RP, Stahl SS, Landis CR. J. Am. Chem. Soc. 2010; 132: 14027
• 10d Worthy AD, Joe CL, Lightburn TE, Tan KL. J. Am. Chem. Soc. 2010; 132: 14757
• 10e Wang X, Buchwald SL. J. Am. Chem. Soc. 2011; 133: 19080
• 11a Lu Z, Wilsily A, Fu GC. J. Am. Chem. Soc. 2011; 133: 8154
• 11b Zultanski SL, Fu GC. J. Am. Chem. Soc. 2011; 133: 15362
• 11c Lundin PM, Fu GC. J. Am. Chem. Soc. 2010; 132: 11027
• 11d Lou S, Fu GC. J. Am. Chem. Soc. 2010; 132: 5010
• 11e Lou S, Fu GC. J. Am. Chem. Soc. 2010; 132: 1264
• 11f Smith SW, Fu GC. J. Am. Chem. Soc. 2008; 130: 12645
• 11g Saito B, Fu GC. J. Am. Chem. Soc. 2008; 130: 6694
• 11h Dai X, Strotman NA, Fu GC. J. Am. Chem. Soc. 2008; 130: 3302
• 11i Son S, Fu GC. J. Am. Chem. Soc. 2008; 130: 2756
• 12a Zhang P, Le H, Kyne RE, Morken JP. J. Am. Chem. Soc. 2011; 133: 9716
• 12b Brozek LA, Ardolino MJ, Morken JP. J. Am. Chem. Soc. 2011; 133: 16778
• 13a López F, Harutyunyan SR, Minnaard AJ, Feringa BL. J. Am. Chem. Soc. 2004; 126: 12784
• 13b López F, Harutyunyan SR, Meetsma A, Minnaard AJ, Feringa BL. Angew. Chem. Int. Ed. 2005; 44: 2752
• 14 Lee K.-s, Brown MK, Hird AW, Hoveyda AH. J. Am. Chem. Soc. 2006; 128: 7182
• 15a Lee S, MacMillan DW. C. J. Am. Chem. Soc. 2007; 129: 15438
• 15b Reiter M, Torssell S, Lee S, MacMillan DW. C. Chem. Sci. 2010; 1: 37
• 15c Shintani R, Hayashi T. Org. Lett. 2011; 13: 350
• 16a d’Augustin M, Palais L, Alexakis A. Angew. Chem. Int. Ed. 2005; 44: 1376
• 16b Hawner C, Li K, Cirriez V, Alexakis A. Angew. Chem. Int. Ed. 2008; 47: 8211
• 16c Hawner C, Müller D, Gremaud L, Felouat A, Woodward S, Alexakis A. Angew. Chem. Int. Ed. 2010; 49: 7769
• 16d May TL, Dabrowski JA, Hoveyda AH. J. Am. Chem. Soc. 2011; 133: 736
• 17 Hamashima Y, Hotta D, Sodeoka M. J. Am. Chem. Soc. 2002; 124: 11240
• 18 Jackowski O, Alexakis A. Angew. Chem. Int. Ed. 2010; 49: 3346
• 19 Murphy KE, Hoveyda AH. Org. Lett. 2005; 7: 1255
• 20a Shintani R, Takatsu K, Takeda M, Hayashi T. Angew. Chem. Int. Ed. 2011; 50: 8656
• 20b Ohmiya H, Makida Y, Li D, Tanabe M, Sawamura M. J. Am. Chem. Soc. 2009; 132: 879
• 21a Akiyama K, Gao F, Hoveyda AH. Angew. Chem. Int. Ed. 2010; 49: 419
• 21b Gao F, McGrath KP, Lee Y, Hoveyda AH. J. Am. Chem. Soc. 2010; 132: 14315
• 21c Gao F, Lee Y, Mandai K, Hoveyda AH. Angew. Chem. Int. Ed. 2010; 49: 8370
• 21d Dabrowski JA, Gao F, Hoveyda AH. J. Am. Chem. Soc. 2011; 133: 4778
• 22 Fujimoto T, Endo K, Tsuji H, Nakamura M, Nakamura E. J. Am. Chem. Soc. 2008; 130: 4492
• 23a Kuwano R, Uchida K.-i, Ito Y. Org. Lett. 2003; 5: 2177
• 23b For other examples of allylation reactions, see: Lu Z, Ma S. Angew. Chem. Int. Ed. 2008; 47: 258
• 24a Trost BM, Zhang Y. J. Am. Chem. Soc. 2006; 128: 4590
• 24b Trost BM, Quancard J. J. Am. Chem. Soc. 2006; 128: 6314
• 24c Kimura M, Futamata M, Mukai R, Tamaru Y. J. Am. Chem. Soc. 2005; 127: 4592
• 25 Seto M, Roizen JL, Stoltz BM. Angew. Chem. Int. Ed. 2008; 47: 6873
• 26a Behenna DC, Stoltz BM. J. Am. Chem. Soc. 2004; 126: 15044
• 26b Trost BM, Xu J. J. Am. Chem. Soc. 2005; 127: 2846
• 26c Mohr JT, Behenna DC, Harned AM, Stoltz BM. Angew. Chem. Int. Ed. 2005; 44: 6924
• 26d McFadden RM, Stoltz BM. J. Am. Chem. Soc. 2006; 128: 7738
• 26e Petrova KV, Mohr JT, Stoltz BM. Org. Lett. 2009; 11: 293
• 26f Day JJ, McFadden RM, Virgil SC, Kolding H, Alleva JL, Stoltz BM. Angew. Chem. Int. Ed. 2011; 50: 6814
• 27 Mohr JT, Nishimata T, Behenna DC, Stoltz BM. J. Am. Chem. Soc. 2006; 128: 11348
• 28 Cheon CH, Kanno O, Toste FD. J. Am. Chem. Soc. 2011; 133: 13248
• 29 Mukherjee S, List B. J. Am. Chem. Soc. 2007; 129: 11336
• 30a Ooi T, Takeuchi M, Kato D, Uematsu Y, Tayama E, Sakai D, Maruoka K. J. Am. Chem. Soc. 2005; 127: 5073
• 30b Hong S, Lee J, Kim M, Park Y, Park C, Kim M.-h, Jew S.-s, Park H.-g. J. Am. Chem. Soc. 2011; 133: 4924
• 31a Spielvogel DJ, Buchwald SL. J. Am. Chem. Soc. 2002; 124: 3500
• 31b Liao X, Stanley LM, Hartwig JF. J. Am. Chem. Soc. 2011; 133: 2088
• 32 Trost BM, Thaisrivongs DA. J. Am. Chem. Soc. 2009; 131: 12056
• 33 Pan S, Endo K, Shibata T. Org. Lett. 2011; 13: 4692
• 34 Reznichenko AL, Emge TJ, Audörsch S, Klauber EG, Hultzsch KC, Schmidt B. Organometallics 2011; 30: 921
• 35a Zhang A, RajanBabu TV. J. Am. Chem. Soc. 2006; 128: 5620
• 35b Mans DJ, Cox GA, RajanBabu TV. J. Am. Chem. Soc. 2011; 133: 5776
• 36 Shirakura M, Suginome M. Angew. Chem. Int. Ed. 2010; 49: 3827
• 37 Palomo C, Oiarbide M, Kardak BG, García JM, Linden A. J. Am. Chem. Soc. 2005; 127: 4154
• 38 Poulsen TB, Jørgensen KA. Chem. Rev. 2008; 108: 2903
• 39 Huang Y, Tokunaga E, Suzuki S, Shiro M, Shibata N. Org. Lett. 2010; 12: 1136
• 40 Momiyama N, Tabuse H, Terada M. J. Am. Chem. Soc. 2009; 131: 12882
• 41 Mukherjee S, Corey EJ. Org. Lett. 2010; 12: 632
• 42 Lin L, Kuang Y, Liu X, Feng X. Org. Lett. 2011; 13: 3868
• 43 Liu W, Chen D, Zhu X.-Z, Wan X.-L, Hou X.-L. J. Am. Chem. Soc. 2009; 131: 8734
• 44 Morandi B, Mariampillai B, Carreira EM. Angew. Chem. Int. Ed. 2011; 50: 1101
• 45a Liang B, Novak T, Tan Z, Negishi E. J. Am. Chem. Soc. 2006; 128: 2770
• 45b Zhu G, Negishi E. Org. Lett. 2007; 9: 2771
• 45c Novak T, Tan Z, Liang B, Negishi E. J. Am. Chem. Soc. 2005; 127: 2838
• 46 Gessner VH, Däschlein C, Strohmann C. Chem.–Eur. J. 2009; 15: 3320
• 47 Pérez M, Fañanás-Mastral M, Bos PH, Rudolph A, Harutyunyan SR, Feringa BL. Nat. Chem. 2011; 3: 377
• 48 López F, van Zijl AW, Minnaard AJ, Feringa BL. Chem. Commun. 2006; 409
• 49 Lee Y, Li B, Hoveyda AH. J. Am. Chem. Soc. 2009; 131: 11625
• 50 Lum T.-K, Wang S.-Y, Loh T.-P. Org. Lett. 2008; 10: 761
• 51a Cesati RR III, de Armas J, Hoveyda AH. J. Am. Chem. Soc. 2004; 126: 96
• 51b Rathgeb X, March S, Alexakis A. J. Org. Chem. 2006; 71: 5737
• 51c Endo K, Ogawa M, Shibata T. Angew. Chem. Int. Ed. 2010; 49: 2410
• 51d Luchaco-Cullis CA, Hoveyda AH. J. Am. Chem. Soc. 2002; 124: 8192
• 51e Wu J, Mampreian DM, Hoveyda AH. J. Am. Chem. Soc. 2005; 127: 4584
• 52a Alexakis A, Albrow V, Biswas K, d’Augustin M, Prieto O, Woodward S. Chem. Commun. 2005; 2843
• 52b Pizzuti MG, Minnaard AJ, Feringa BL. Org. Biomol. Chem. 2008; 6: 3464
• 52c May TL, Brown MK, Hoveyda AH. Angew. Chem. Int. Ed. 2008; 47: 7358
• 52d Vuagnoux-d’Augustin M, Alexakis A. Tetrahedron Lett. 2007; 48: 7408
• 52e Gremaud L, Alexakis A. Angew. Chem. Int. Ed. 2012; 51: 794
• 53a Lautens M, Renaud J.-L, Hiebert S. J. Am. Chem. Soc. 2000; 122: 1804
• 53b Lautens M, Hiebert S. J. Am. Chem. Soc. 2004; 126: 1437
• 53c Priego J, Mancheño OG, Cabrera S, Arrayás RG, Llamas T, Carretero JC. Chem. Commun. 2002; 2512
• 53d Endo K, Tanaka K, Ogawa M, Shibata T. Org. Lett. 2011; 13: 868
• 53e Lautens M, Hiebert S, Renaud J.-L. Org. Lett. 2000; 2: 1971
• 54a Nagib DA, Scott ME, MacMillan DW. C. J. Am. Chem. Soc. 2009; 131: 10875
• 54b Allen AE, MacMillan DW. C. J. Am. Chem. Soc. 2010; 132: 4986
• 55 Furukawa T, Nishimine T, Tokunaga E, Hasegawa K, Shiro M, Shibata N. Org. Lett. 2011; 13: 3972