Akiyama-Terada Catalyst

03 April, 2015 / by SK / in Reactions

5317

General Characteristics

The phosphoric acids containing an appropriately substituted BINOL backbone function as chiral Brønsted acid catalysts that can promote a wide range of stereoselective reactions.

Reported independently in 2004 by the laboratories of Takahiko Akimaya (of Gakushuin University, Japan) and Masahiro Terada (Tohoku University, Japan), these catalysts are called the Akiyama-Terada catalysts.

A number of modified catalysts have been reported more recently, including the imide version and the chiral counter anion version. The versatility of these catalysts makes them one of the most popular organocatalyst classes known today.

General References

Akiyama, T.; Itoh, J.; Yokota, K.; Fuchibe, K. Angew. Chem. Int. Ed. 2004, 43, 1566. DOI: 10.1002/anie.200353240
Uraguchi, D.; Terada, M. J. Am. Chem. Soc.2004, 126, 5365. DOI: 10.1021/ja0491533

Akiyama, T.; Itoh, J.; Fuchibe, K. Adv. Synth. Catal. 2006, 348, 999. DOI: 10.1002/adsc.200606074
Akiyama, T. Chem. Rev.2007, 107, 5744. DOI: 10.1021/cr068374j
Doyle, A. G.; Jacobsen, E. N. Chem. Rev.2007, 107, 5713. DOI: 10.1021/cr068373r
Terada, M. Chem. Commun.2008, 4097. DOI: 10.1039/B807577H
Adair, G.; Mukherjee, S.; List, B. Aldrichimica Acta2008, 41, 31. [website]
Zamfir, A.; Schenker, S.; Freund, M.; Tsogoeva, S. B. Org. Biomol. Chem.2010, 8, 5262. DOI: 10.1039/C0OB00209G
Terada, M. Bull. Chem. Soc. Jpn.2010, 83, 101. doi:10.1246/bcsj.20090268
Terada, M. Synthesis2010, 1929. DOI: 10.1055/s-0029-1218801
Rueping, M.; Kuenkel, A.; Atodiresei, I. Chem. Soc. Rev.2011, 40, 4539. DOI: 10.1039/C1CS15087A
Akiyama, T. J. Synth. Org. Chem. Jpn. 2011, 69, 913. doi:10.5059/yukigoseikyokaishi.69.913
Lv, F.; Liu, S.; Hu, W. Asian J. Org. Chem.2013, 2, 824. DOI: 10.1002/ajoc.201300097

Lacour, J.; Moraleda, D. Chem. Commun. 2009, 7073. DOI: 10.1039/b912530b
Phipps, R. J.; Hamilton, G. L.; Toste, F. D. Nat. Chem.2012, 4, 603. doi:10.1038/nchem.1405
Mahlau, M.; List, B. Angew. Chem. Int. Ed.2013, 52, 518. DOI: 10.1002/anie.201205343

Reaction Mechanism
Examples

The phosphoric acid-catalyzed reactions are by no means limited to additions to imines. An example shown below is the asymmetric Nazarov cyclization.^[1]

In the asymmetric α-allylation of aldehydes via π-allylpalladium, the phosphoric acid and the palladium can coexist and cooperate to achieve the synthesis of all-carbon quaternary stereogenic centers in high enantioselectivity.^[2]

An example in which the phosphoric acid was used as the counter anion of a gold catalyst.^[3] This concept is helpful when neutral chiral ligands are ineffective in creating the chiral environment.

Experimental Procedure
Experimental Tips
References

[1] Rueping, M.; Ieawsuwan, W.; Antonchick, A. P.; Nachtsheim, B. J. Angew. Chem. Int. Ed. 2007, 46,
2097. DOI: 10.1002/anie.200604809 [2] Mukherjee, S.; List, B. J. Am. Chem. Soc. 2007, 129, 11336. DOI: 10.1021/ja074678r [3] Hamilton, G. L.; Kang, E. J.; Mba, M.; Toste, F. D. Science 2007, 317, 496. DOI:10.1126/science.1145229

Related Reactions
Related Books

[amazonjs asin=”B00BLRNHYC” locale=”US” title=”Development of Novel Hydrogen-Bond Donor Catalysts (Springer Theses)”]

[amazonjs asin=”3527332367″ locale=”US” title=”Comprehensive Enantioselective Organocatalysis: Catalysts, Reactions, and Applications, 3 Volume Set”]

[amazonjs asin=”3709111625″ locale=”US” title=”Asymmetric Organocatalysis in Natural Product Syntheses (Progress in the Chemistry of Organic Natural Products)”]