Electrocatalysis in the Lin Lab
Our discoveries in the realm of electrocatalysis can be attributed to a strong grasp of the physical and mechanistic phenomena governing the design of electrocatalytic systems. In the past few years, we have employed electrocatalysis as a general approach for the difunctionalization of alkenes by compounding upon lessons learned from our previous findings. Our early research efforts led to the development of two generations of alkene diazidation reactions using transition metal and organic radical catalysis, respectively. We further applied this electrocatalytic radical mechanism to effect chemo- and regioselective heterodifunctionalization of alkenes, leading to the development of a variety of reactions including halotrifluoromethylation, haloalkylation and azidophosphinoylation. Importantly, we have also demonstrated enantioselective electrocatalysis in the context of cyanofunctionalization reactions. These developments showcase the generality of our electrocatalytic strategy in the context of alkene functionalization. We anticipate that electrocatalysis will play an increasingly important role in the ongoing Renaissance of synthetic electrochemistry.
Representative Publications
Novaes, L. F. T.; Wang, Y.; Liu, J.; Riart-Ferrer, X.; Lee, W.-C. C.; Fu, N.; Ho, J. S. K.; Zhang, X. P.*; Lin, S.* “Electrochemical Diazidation of Alkenes Catalyzed by Manganese Porphyrin Complexes with Second-Sphere Hydrogen-Bond Donors.” ACS Catal. 2022, 12, 14106–14112. DOI: 10.1021/acscatal.2c05186 [html]
Wu, X.; Gannett, C. N.; Liu, J.; Zeng, R.; Novaes, L. F. T.; Wang, H.; Abruña, H. D.*; Lin, S.* “Intercepting Hydrogen Evolution with Hydrogen-Atom Transfer: Electron-Initiated Hydrofunctionalization of Alkenes.” J. Am. Chem. Soc. 2022, 144, 17783–17791. DOI: 10.1021/jacs.2c08278 [html]
Novaes, L. F. T.; Liu, J.; Shen, Y.; Lu, L.; Meinhardt, J. M.; Lin, S.* “Electrocatalysis as an Enabling Technology for Organic Synthesis.” Chem. Soc. Rev. 2021, 50, 7941–8002. DOI: 10.1039/D1CS00223F [html] Invited review.
Nelson, H.*; Siu. J.C.; Saha, A.; Cascio, D.; Wu, S.-B.; Lu, C.; Rodriguez, J. A.; Houk, K. N.*; Lin, S.* “Isolation and X-ray Crystal Structure of an Electrogenerated TEMPO–N3 Charge-Transfer Complex.” Org. Lett. 2021, 23, 454–458. DOI: 10.1021/acs.orglett.0c03966 [html]
Song, L.; Fu, N.; Ernst, B. G.; Lee, W. H.; Lin, S. “Dual Electrocatalysis Enables Enantioselective Hydrocyanation of Conjugated Alkenes” Nat. Chem. 2020. DOI: 10.1038/s41557-020-0469-5 [html] [open full-text access]
Nelson, H.; Siu. J.C.; Saha, A.; Cascio, D.; Wu, S-B.; Lu, C.; Rodriguez, J. A.; Houk, K. N.; Lin, S. “Isolation and X-ray Crystal Structure of an Electrogenerated TEMPO–N3 Charge-Transfer Complex” Chem Rxiv Preprint. 2020. DOI: 10.26434/chemrxiv.12102054.v2 [html]
Siu, J. C.; Fu, N.; Lin, S. “Catalyzing Electrosynthesis: A Homogeneous Electrocatalytic Approach to Reaction Discovery” Acc. Chem. Res. 2020, 53, 547-560. DOI: 10.1021/acs.accounts.9b00529 [html]
Novaes, L. F. T.; Lin, S. “Electrocatalytic Diazidation of Alkenes” Trends in Chem. 2020, 2, 84-85. DOI: 10.1016/j.trechm.2019.10.005 [html]
Fu, N.; Song, L.; Liu, J.; Shen, Y.; Siu, J. C.; Lin, S. “New Bisoxazoline Ligands Enable Enantioselective Electrocatalytic Cyanofunctionalization of Vinylarenes” JACS 2019, 141, 14480-14485. DOI: 10.1021/jacs.9b03296 [html]
Lu, L.; Fu, N.; Lin, S. “Three-Component Chlorophosphinoylation of Alkenes via Anodically Coupled Electrolysis” Synlett 2019, 30, 1199-1203. DOI: 10.1055/s-0039-1689934 [html]
An invited contribution to the Cluster Electrochemical Synthesis and Catalysis
(25) Siu, J. C.; Parry, J. B.; Lin, S. “Aminoxyl-Catalyzed Electrochemical Diazidation of Alkenes Mediated by a Metastable Charge-Transfer Complex” J. Am. Chem. Soc. 2019, 141, 2825-2831. DOI: 10.1021/jacs.8b13192 [html]
Fu, N.; Shen, Y.; Allen, A.R.; Song, L.; Ozaki, A.; Lin, S. “Mn-catalyzed Electrochemical Chloroalkylation of Alkenes” ACS Catal. 2019, 9, 746-754. DOI: 10.1021/acscatal.8b03209 [html]
Siu, J. C.; Sauer, G. S.; Saha, A.; Macey, R. L.; Fu, N.; Chauvirie, T.; Lancaster, K. L.; Lin, S. “Electrochemical Azidooxygenation of Alkenes Mediated by a TEMPO–N3Charge-Transfer Complex.” J. Am. Chem. Soc. 2018, 40, 12511-12520. DOI: 10.1021/jacs.8b06744 [html]
Fu, N.; Sauer, G. S.; Lin, S. “A general, electrocatalytic approach to the synthesis of vicinal diamines.” Nat. Protoc. 2018, 13, 1725-1743. DOI: 10.1038/s41596-018-0010-0 [PDF][HTML]
Ye, K.; Pombar, G.; Fu, N.; Sauer, G. S.; Keresztes, I.; Lin, S. “Anodically Coupled Electrolysis for the Heterodifunctionalization of Alkenes” J. Am. Chem. Soc. 2018, 140, 2438–2441. DOI: 10.1021/jacs.7b13387 [html]
Parry, J. B .; Fu, N.; Lin, S. “Electrocatalytic Difunctionalization of Olefins as a General Approach to the Synthesis of Vicinal Diamines.”, Synlett 2018, 29, 257-265 , DOI: 10.1055/s-0036-1591749 (Invited Account). [html]
Fu, N.; Sauer, G. S.; Lin, S. “Electrocatalytic Radical Dichlorination of Alkenes with Nucleophilic Chlorine Sources.”, J. Am. Chem. Soc. 2017, 139, 15548-15553, DOI: 10.1021/jacs.7b09388. [html]
Fu, N.; Sauer, G. S.; Saha, A.; Loo, A; Lin, S. “Metal-catalyzed electrochemical diazidation of alkenes”, Science 2017, 357, 575-579. [Abstract][Full Text]
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