Nucleophilic Substitution of the Hydroxyl Group in Stereogenic Alcohols with Chirality Transfer

Abstract

A brief overview of the development of direct substitution of the hydroxyl (OH) group of alcohols in our research group is presented. By applying a Brønsted acid, an intramolecular substitution of the OH group in stereogenic alcohols with chirality transfer was achieved. Noteworthy, the intramolecular substitution has a wide scope in respect to both the nucleophile and also the nucleofuge. A mechanistic study by both experiments and DFT calculations revealed a unique reaction pathway in which the Brønsted acid operates in a bifunctional manner to promote an S_N2-type reaction mechanism.

Key words

green chemistry - Brønsted acid/base catalysis - chirality transfer - nucleophilic substitutions - asymmetric synthesis - mechanistic studies - DFT calculations

• References

• 1a Mayr H, Kempf B, Ofial AR. Acc. Chem. Res. 2003; 36: 66
• 1b Emer E, Riccardo S, Capdevila MG, Petruzziello D, Vincentiis FD, Cozzi PG. Eur. J. Org. Chem. 2011; 647
• 1c Tamaru Y. Eur. J. Org. Chem. 2005; 2647
• 1d Muzart J. Eur. J. Org. Chem. 2007; 3077
• 1e Muzart J. Tetrahedron 2005; 61: 4179
• 1f Biswas S, Samec JS. M. Chem. Asian J. 2013; 8: 974
• 2 Anastas PT, Warner JC. Green Chemistry: Theory and Practice . Oxford University Press; USA: 2000
• 3a Krische M. Angew. Chem. Int. Ed. 2009; 48: 34
• 3b Kumagai N, Shibasaki M. Angew. Chem. Int. Ed. 2011; 50: 4760
• 3c Dobereiner GE, Crabtree RH. Chem. Rev. 2010; 110: 681
• 3d Guillena G, Ramon DJ, Yus M. Chem. Rev. 2010; 110: 1611
• 4a Galkin MV, Sawadjoon S, Rohde V, Dawange M, Samec JS. M. ChemCatChem 2014; 6: 179
• 4b Galkin MV, Samec JS. M. ChemSusChem 2014; 7: 2154
• 4c Dawange M, Galkin MV, Samec JS. M. ChemCatChem 2015; 7: 401
• 4d Galkin MV, Dahlstrand C, Samec JS. M. ChemSusChem 2015; 8: 2142
• 4e Sawadjoon S, Lundstedt A, Samec JS. M. ACS Catal. 2013; 3: 635
• 5a Sawadjoon S, Sjöberg PJ. R, Orthaber A, Matsson O, Samec JS. M. Chem. Eur. J. 2014; 20: 1520
• 5b Sawadjoon S, Sjöberg PJ. R, Samec JS. M. Organometallics 2014; 33: 249
• 6 Kawai N, Jean-Marie L, Ohmi M, Uenishi J. J. Org. Chem. 2006; 71: 4530
• 7a Aponick A, Biannic B. Org. Lett. 2011; 13: 1330
• 7b Ghebreghiorgis T, Biannic B, Kirk BH, Aponick A, Ess DH. J. Org. Chem. 2013; 78: 7664
• 7c Aponick A, Li C.-Y, Biannic B. Org. Lett. 2008; 10: 669
• 7d Biannic B, Aponick A. Eur. J. Org. Chem. 2011; 6605
• 7e Paioiti PH, Aponick PH. Top. Curr. Chem. 2015; 357: 63
• 8a Mukherjee P, Widenhoefer RA. Chem. Eur. J. 2013; 19: 3437
• 8b Mukherjee P, Widenhoefer RA. Org. Lett. 2011; 13: 1334
• 8c Mukherjee P, Widenhoefer RA. Org. Lett. 2010; 12: 1184
• 9 Ghebreghiorgis T, Biannic B, Kirk BH, Ess DH, Aponick A. J. Am. Chem. Soc. 2012; 134: 16307
• 10 Bunrit A, Dahlstrand C, Olsson SK, Srifa P, Huang G, Orthaber A, Sjörberg P, Biswas S, Himo F, Samec JS. M. J. Am. Chem. Soc. 2015; 137: 4646
• 11a Simón L, Goodman JM. J. Am. Chem. Soc. 2008; 130: 8741
• 11b Marcelli T, Hammar P, Himo F. Chem. Eur. J. 2008; 14: 8562
• 11c Yamanaka M, Itoh J, Fuchibe K, Akiyama T. J. Am. Chem. Soc. 2007; 129: 6756
• 11d Simón L, Goodman JM. J. Am. Chem. Soc. 2009; 131: 4070
• 11e Chen D.-F, Han Z.-Y, Zhou X.-L, Gong L.-Z. Acc. Chem. Res. 2014; 47: 2365
• 11f Reuping M, Kuenkel A, Atodiresei I. Chem. Soc. Rev. 2011; 40: 4539