Fu's Planar DMAP

4-(Dimethylamino)pyridine (DMAP) is a nucleophilic catalyst frequently used for the acylation of alcohols and the rearrangement of O-acylated enolates. Due to the need for an enantioselective version of this catalyst, Gregory Fu π-complexed the heterocycle with a metal and added a 2-substituent to the ring.^: 5577 This resulted in a planar chiral set of enantioselective DMAP analogs.

As of 2018,^[update] at least two such catalysts were commercially available: DMAPC₅Ph₅, a 1,2,3,4,5-pentaphenylferrocene-fused DMAP derivative, and PPY*, a 1,2,3,4,5-pentamethylferrocene-fused 4-pyrrolidinylpyridine derivative.^: 5578^{: 542–543} A drawback of these catalysts is their limited production volume, as the 1996 synthesis route produces a racemate, requiring resolution via chiral HPLC. In 2020, a high-yield enantioselective synthesis of the two commercial catalysts, amongst other ferrocene-fused 4-dialkylaminopyridines, was achieved.

References

1 2 Wurz, Ryan P. (1 December 2007). "Chiral Dialkylaminopyridine Catalysts in Asymmetric Synthesis". Chemical Reviews. 107 (12): 5570–5595. doi:10.1021/cr068370e. PMID 18072804.
1 2 Fu, Gregory C. (2004-08-01). "Asymmetric Catalysis with "Planar-Chiral" Derivatives of 4-(Dimethylamino)pyridine". Accounts of Chemical Research. 37 (8): 542–547. doi:10.1021/ar030051b. ISSN 0001-4842.
↑ "Metal Catalysts for Organic Synthesis including Organocatalysts" (PDF). Strem Chemicals. 2018. pp. 76, 79.
1 2 Bernardo, Olaya; González‐Pelayo, Silvia; López, Luis A. (18 March 2022). "Synthesis and Applications of Ferrocene‐Fused Nitrogen Heterocycles". European Journal of Inorganic Chemistry. 2022 (8). doi:10.1002/ejic.202100911.
↑ Yoshida, Kazuhiro; Liu, Qiang; Yasue, Risa; Wada, Shiro; Kimura, Ryosuke; Konishi, Takuma; Ogasawara, Masamichi (3 January 2020). "Versatile and Enantioselective Preparation of Planar-Chiral Metallocene-Fused 4-Dialkylaminopyridines and Their Application in Asymmetric Organocatalysis". ACS Catalysis. 10 (1): 292–301. doi:10.1021/acscatal.9b04438.

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[Wurz2007-1] 1 2 Wurz, Ryan P. (1 December 2007). "Chiral Dialkylaminopyridine Catalysts in Asymmetric Synthesis". Chemical Reviews. 107 (12): 5570–5595. doi:10.1021/cr068370e. PMID 18072804.

[Fu2004-2] 1 2 Fu, Gregory C. (2004-08-01). "Asymmetric Catalysis with "Planar-Chiral" Derivatives of 4-(Dimethylamino)pyridine". Accounts of Chemical Research. 37 (8): 542–547. doi:10.1021/ar030051b. ISSN 0001-4842.

[Strem2018-3] "Metal Catalysts for Organic Synthesis including Organocatalysts" (PDF). Strem Chemicals. 2018. pp. 76, 79.

[Bernando2022-4] 1 2 Bernardo, Olaya; González‐Pelayo, Silvia; López, Luis A. (18 March 2022). "Synthesis and Applications of Ferrocene‐Fused Nitrogen Heterocycles". European Journal of Inorganic Chemistry. 2022 (8). doi:10.1002/ejic.202100911.

[Yoshida2020-5] Yoshida, Kazuhiro; Liu, Qiang; Yasue, Risa; Wada, Shiro; Kimura, Ryosuke; Konishi, Takuma; Ogasawara, Masamichi (3 January 2020). "Versatile and Enantioselective Preparation of Planar-Chiral Metallocene-Fused 4-Dialkylaminopyridines and Their Application in Asymmetric Organocatalysis". ACS Catalysis. 10 (1): 292–301. doi:10.1021/acscatal.9b04438.