Ruthenium-Catalyzed Asymmetric Dehydrative Allylic Cyclization of Five-Membered Chalcogen Heteroaromatics

Abstract

The asymmetric dehydrative intramolecular allylation reactions of furan and thiophene were performed using a cationic cyclopentadienyl-ruthenium (CpRu) complex of a chiral pyridine carboxylic acid, namely Cl-Naph-PyCOOH. Both furan and thiophene tethered with an allylic alcohol gave the corresponding bicyclic compounds in high yields and enantioselectivities using 0.1–5 mol% of the catalyst. The reaction was found to proceed via a similar enantioface selection mechanism to that previously reported by our group, which involved halogen and hydrogen bond formation, in addition to the generation of an intermediate σ-allyl complex.

Keywords

furan - thiophene - dehydrative allylation - ruthenium - asymmetric reaction

Publikationsverlauf

Eingereicht: 15. März 2021

Angenommen nach Revision: 07. Juni 2021

Accepted Manuscript online:
07. Juni 2021

Artikel online veröffentlicht:
20. Juli 2021

• References

• 1a Kappe OC, Murphree SS, Padwa A. Tetrahedron 1997; 53: 14179
• 1b Merkushev AA. Chem. Heterocycl. Compd. 2016; 52: 359
• 1c Montagnon T, Kalaitzakis D, Triantafyllakis M, Stratakis M, Vassilikogiannakis G. Chem. Commun. 2014; 50: 15480
• 1d Lipshutz HB. Chem Rev. 1986; 86: 795
• 1e Hao H.-D, Trauner D. J. Am. Chem. Soc. 2017; 139: 4117
• 2a Lee CJ, Cha JK. Tetrahedron 2000; 56: 10175
• 2b Lee CJ, Cha JK. J. Am. Chem. Soc. 2001; 123: 3243
• 2c Brousseau J, Xolin A, Barriault L. Org. Lett. 2019; 21: 1347
• 2d Stork G, Yamashita A, Adams J, Schulte GR, Chesworth R, Miyazaki Y, Farmer JJ. J. Am. Chem. Soc. 2009; 131: 11402
• 2e Ginn DJ, Padwa A. Org. Lett. 2002; 4: 1515
• 3a Menut C, Pierre C, Hnawia E, Agnaniet H, Waikedre J, Fruchier A. Flavour Frag. J. 2005; 20: 621
• 3b Cimino G, Stefano DS, Guerriero A, Minale L. Tetrahedron Lett. 1975; 17: 1425
• 3c Garrido L, Zubıa E, Ortega JM, Salva J. J. Nat. Prod. 1997; 60: 794
• 3d Kazlauskas R, Murphy TP, Wells JR. Tetrahedron Lett. 1996; 37: 4951
• 3e Topcu G, Eris C. J. Nat. Prod. 1997; 60: 1045
• 3f Gustafson K, Andersen JR, He C.-H, Clardy J. Tetrahedron Lett. 1985; 26: 2521
• 3g Patil DA, Freyer JA, Killmer L, Offen P, Carte B, Jurewicz JA, Johnson KR. Tetrahedron Lett. 1997; 38: 5047
• 3h Marion F, Williams ED, Patrick O, Hollander I, Mallon R, Kim CS, Roll MD, Feldberg L, Soest VR, Andersen JR. Org. Lett. 2006; 8: 321
• 3i Kobayashi J, Watanabe D, Kawasaki N, Tsuda M. J. Org. Chem. 1997; 62: 9236
• 4 Kondoh A, Ota Y, Komuro T, Egawa F, Kanomata K, Terada M. Chem. Sci. 2016; 7: 1057
• 5 Conrad CJ, Jongrock K, Brian NL, MacMillan DW. C. J. Am. Chem. Soc. 2009; 131: 11640
• 6a Jui NT, Lee EC. Y, MacMillan DW. C. J. Am. Chem. Soc. 2010; 132: 10015
• 6b Gao F, Lee Y, Mandai K, Hoveyda AH. Angew. Chem. Int. Ed. 2010; 49: 8370

First report:
• 7a Tanaka S, Seki T, Kitamura M. Angew. Chem. Int. Ed. 2009; 48: 8948

Pyrrole allylation:
• 7b Iwase S, Suzuki Y, Tanaka S, Kitamura M. Org. Lett. 2020; 22: 1929

Mechanism:
• 7c Tanaka S, Suzuki Y, Kimura T, Kitamura M. Bull. Chem. Soc. Jpn. 2019; 92: 1707
• 7d Suzuki Y, Iwase S, Ratanasak M, Hasegawa J, Tanaka S, Kitamura M. Bull. Chem. Soc. Jpn. 2021; 94: 440
• 8a Trost BM, Crawley M. Chem. Rev. 2003; 103: 2921
• 8b Mohr JT, Stoltz BM. Chem. Asian J. 2007; 2: 1476
• 8c Lu Z, Ma S. Angew. Chem. Int. Ed. 2008; 47: 258
• 9 Lee JC, Cha JK. Tetrahedron 2000; 56: 10175
• 10 Wang X, Zhu L, Chen S, Xu X, Au C.-T, Qiu R. Org. Lett. 2015; 17: 5228
• 11 Cavallo G, Metrangolo P, Milani R, Pilati T, Priimagi A, Resnati G, Terraneo G. Chem. Rev. 2016; 116: 2478
• 12 For details, see the Supporting Information.