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DOI: 10.1055/a-1406-0484
Titanium: A Unique Metal for Radical Dehydroxylative Functionalization of Alcohols
We thank the National Natural Science Foundation of China (22071084, 21772072) for financial support.
Abstract
The dehydroxylative functionalization of alcohols is synthetic appealing, but it remains a long-term challenge in the synthetic community. Low-valent titanium has shown the power to produce carbon radicals from alcohols via homolytic cleavage of the C–OH bonds and thus offers the potential to overcome this problem. In this perspective manuscript, we summarized the recent advance on radical dehydroxylative transformation of alcohols either promoted or catalyzed by titanium. The limitation and outlook of the studies in this field are also provided.
1 Introduction
2 Recent Developments in Dehydroxylative Functionalization of Alcohols
2.1 Stoichiometric Titanium Complexes Mediated Homolysis of Alcohols
2.2 Radical Dehydroxylative Functionalization of Alcohols by Ti Catalysis
3 Summary and Outlook
Publication History
Received: 10 January 2021
Accepted after revision: 04 March 2021
Accepted Manuscript online:
04 March 2021
Article published online:
07 April 2021
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References
- 1 Bermudez E, Mangum JB, Asgharian B, Wong BA, Reverdy EE, Janszen DB, Hext PM, Warheit DB, Everitt JI. Toxicol. Sci. 2002; 70: 86
- 2 Cahours MA. Ann. Chim. Phys. 1861; 62: 257
- 3 Herman DF, Nelson WK. J. Am. Chem. Soc. 1953; 75: 3877
- 4 Kealy TJ, Pauson PL. Nature 1951; 168: 1039
- 5 Wilkinson G, Birmingham JM. J. Am. Chem. Soc. 1954; 76: 4281
- 6 For the fundamental patterns of titanium, see: Mikami K, Matsumoto Y, Shiono T. "Organometallic Complexes of Titanium" in Science of Synthesis, Vol. 2; Imamoto, T.; Noyori, R., Thieme, Stuttgart:; 2003: 457-679.
- 7 Enemærke JR, Larsen J, Skrydstrup T, Daasbjerg K. J. Am. Chem. Soc. 2004; 126: 7853
- 8 Enemærke JR, Larsen J, Skrydstrup T, Daasbjerg K. Organometallics 2004; 23: 1866
- 9a Streuff J. Chem. Rec. 2014; 14: 1100
- 9b Morcillo SP, Miguel D, Campaña AG, Álvarez de Cienfuegos L, Justicia J, Cuerva JM. Org. Chem. Front. 2014; 1: 15
- 9c Rosales A, Rodríguez-García I, Muñoz-Bascón J, Roldan-Molina E, Padial NM, Morales LP, García-Ocaña M, Oltra JE. Eur. J. Org. Chem. 2015; 4567
- 9d Okamoto S. Chem. Rec. 2016; 16: 857
- 9e Castro-Rodriguez M, Rodriguez-Garcia I, Rodriguez-Maecker RN, Pozo-Morales L, Oltra JE, Martinez AR. Org. Process Res. Dev. 2017; 21: 911
- 9f Botubol-Ares JM, Durán-Peña MJ, Hansonb JR, Hernández-Galána R, Collado IG. Synthesis 2018; 50: 2163
- 9g McCallum T, Wu X, Lin S. J. Org. Chem. 2019; 84: 14369
- 9h Beaumier EP, Pearce AJ, See XY, Tonks IA. Nat. Rev. Chem. 2019; 3: 15
- 9i Fermi A, Gualandi A, Bergamini G, Cozzi PG. Eur. J. Org. Chem. 2020; 6955
- 9j Manßen M, Schafer LL. Chem. Soc. Rev. 2020; 49: 6947
- 10 Davidson PJ, Lappert MF, Pearce R. Chem. Rev. 1976; 76: 219
- 11a Nugent WA, RajanBabu TV. J. Am. Chem. Soc. 1988; 110: 8561
- 11b RajanBabu TV, Nugent WA. J. Am. Chem. Soc. 1989; 111: 4525
- 12a Boucher-Jacobs C, Liu P, Nicholas KM. Organometallics 2018; 37: 2468
- 12b Bandari C, Nicholas KM. J. Org. Chem. 2020; 85: 3320
- 13a Steffensmeier E, Nicholas KM. Chem. Commun. 2018; 54: 790
- 13b Griffin SE, Schafer LL. Inorg. Chem. 2020; 59: 5256
- 14 Crevier TJ, Mayer JM. J. Am. Chem. Soc. 1997; 119: 8485
- 15 Larsen DB, Petersen AR, Dethlefsen JR, Teshome A, Fristrup P. Chem. Eur. J. 2016; 22: 16621
- 16 Sato M, Oshima K. Chem. Lett. 1982; 11: 157
- 17 Radical Reactions in Organic Synthesis. Zard SZ. Oxford; New York: 2003
- 19 van Tamelen EE, Schwartz MA. J. Am. Chem. Soc. 1965; 87: 3277
- 20 McMurry JE, Silvestri MG, Fleming MP, Hoz T, Grayston MW. J. Org. Chem. 1978; 43: 3249
- 21 Diéguez HR, López A, Domingo V, Arteaga JF, Dobado JA, Herrador MM, Quílez del Moral JF, Barrero AF. J. Am. Chem. Soc. 2010; 132: 254
- 22 Suga T, Shimazu S, Ukaji Y. Org. Lett. 2018; 20: 5389
- 23 Suga T, Ukaji Y. Org. Lett. 2018; 20: 7846
- 24a Pang X, Peng X, Shu X.-Z. Synthesis 2020; 52: 3751
- 24b He R.-D, Li C.-L, Pan Q.-Q, Guo P, Liu X.-Y, Shu X.-Z. J. Am. Chem. Soc. 2019; 141: 12481
- 24c Tian Z.-X, Qiao J.-B, Xu G.-L, Pang X, Qi L, Ma W.-Y, Zhao Z.-Z, Duan J, Du Y.-F, Su P.-F, Liu X.-Y, Shu X.-Z. J. Am. Chem. Soc. 2019; 141: 7637
- 24d Duan J, Wang K, Xu G.-L, Kang S, Qi L, Liu X.-Y, Shu X.-Z. Angew. Chem. Int. Ed. 2020; 59: 23083
- 25 Yan XB, Li CL, Jin WJ, Guo P, Shu X.-Z. Chem. Sci. 2018; 9: 4529
- 26 Duan J, Du Y.-F, Pang X, Shu X.-Z. Chem. Sci. 2019; 10: 8706
- 27a Jia XG, Guo P, Duan J, Shu X.-Z. Chem. Sci. 2018; 9: 640
- 27b Guo P, Wang K, Jin W.-J, Xie H, Qi L, Liu X.-Y, Shu X.-Z. J. Am. Chem. Soc. 2021; 143: 513
- 28 Xie H, Guo J, Wang Y.-Q, Wang K, Guo P, Su P.-F, Wang X, Shu X.-Z. J. Am. Chem. Soc. 2020; 142: 16787
- 29 Zheng X, Dai X.-J, Yuan H.-Q, Ye C.-X, Ma J, Huang P.-Q. Angew. Chem. Int. Ed. 2013; 52: 3494