Royer, J. Chiral Amine Synthesis: Methods, Developments and Applications (Wiley, 2010).

Vitaku, E., Smith, D. T. & Njardarson, J. T. Analysis of the structural diversity, substitution patterns and frequency of nitrogen heterocycles among US FDA approved pharmaceuticals. J. Med. Chem. 57, 10257–10274 (2014).

Article  CAS  Google Scholar 

Li, M.-L., Yu, J.-H., Li, Y.-H., Zhu, S.-F. & Zhou, Q.-L. Highly enantioselective carbene insertion into N–H bonds of aliphatic amines. Science 366, 990–994 (2019).

Article  ADS  CAS  Google Scholar 

Xi, Y.-M., Ma, S.-J. & Hartwig, J. F. Catalytic asymmetric addition of an amine N–H bond across internal alkenes. Nature 588, 254–260 (2020).

Article  ADS  CAS  Google Scholar 

Chen, C.-Y., Peters, J. C. & Fu, G. C. Photoinduced copper-catalysed asymmetric amidation via ligand cooperativity. Nature 596, 250–256 (2021).

Article  ADS  CAS  Google Scholar 

Hameed, A., Al-Rashida, M. & Shah, M. R. α-Tertiary Amines en Route to Natural Products (Elsevier, 2021).

Hager, A. et al. Synthetic approaches towards alkaloids bearing α-tertiary amines. Nat. Prod. Rep. 33, 491–522 (2016).

Article  CAS  Google Scholar 

Talele, T. T. Opportunities for tapping into three-dimensional chemical space through a quaternary carbon. J. Med. Chem. 63, 13291–13315 (2020).

Article  CAS  Google Scholar 

Pronin, S. V., Reiher, C. A. & Shenvi, R. A. Stereoinversion of tertiary alcohols to tertiary-alkyl isonitriles and amines. Nature 501, 195–199 (2013).

Article  ADS  CAS  Google Scholar 

Shibasaki, M. & Kanai, M. Asymmetric synthesis of tertiary alcohols and α-tertiary amines via Cu-catalyzed C-C bond formation to ketones and ketimines. Chem. Rev. 108, 2853–2873 (2008).

Article  CAS  Google Scholar 

Yin, Q., Shi, Y.-J., Wang, J.-X. & Zhang, X.-M. Direct catalytic asymmetric synthesis of α-chiral primary amines. Chem. Soc. Rev. 49, 6141–6153 (2020).

Article  Google Scholar 

Xu, Y.-Z., Wang, J.-J., Deng, G.-J. & Shao, W. Recent advances in the synthesis of chiral α-tertiary amines via transition-metal catalysis. Chem. Commun. 59, 4099–4114 (2023).

Article  CAS  Google Scholar 

Wu, Y.-W., Hu, L., Li, Z. & Deng, L. Catalytic asymmetric umpolung reactions of imines. Nature 523, 445–450 (2015).

Article  ADS  CAS  Google Scholar 

Chen, J.-J. et al. Enantioconvergent Cu-catalysed N-alkylation of aliphatic amines. Nature 618, 294–300 (2023).

Article  ADS  CAS  Google Scholar 

Ye, C.-X., Shen, X., Chen, S.-M. & Meggers, E. Stereocontrolled 1,3-nitrogen migration to access chiral α-amino acids. Nat. Chem. 14, 566–573 (2022).

Article  CAS  Google Scholar 

Xu, P., Xie, J.-J., Wang, D.-S. & Zhang, X. P. Metalloradical approach for concurrent control in intermolecular radical allylic C−H amination. Nat. Chem. 15, 498–507 (2023).

Article  CAS  Google Scholar 

Keith, J. M. & Jacobsen, E. N. Asymmetric hydrocyanation of hydrazones catalyzed by lanthanide-PYBOX complexes. Org. Lett. 6, 153–155 (2004).

Article  CAS  Google Scholar 

Detz, R. J., Abiri, Z., Remi, G., Hiemstra, H. & van Maarseveen, J. H. Enantioselective copper-catalysed propargylic substitution: synthetic scope study and application in formal total syntheses of (+)-anisomycin and (−)-cytoxazone. Chem. Eur. J. 17, 5921–5930 (2011).

Article  CAS  Google Scholar 

Nishikawa, D., Hirano, K. & Miura, M. Asymmetric synthesis of α‑aminoboronic acid derivatives by copper-catalyzed enantioselective hydroamination. J. Am. Chem. Soc. 137, 15620–15623 (2015).

Article  CAS  Google Scholar 

Liu, R.-R. et al. Palladium/l‑proline-catalyzed enantioselective α‑arylative desymmetrization of cyclohexanones. J. Am. Chem. Soc. 138, 5198–5201 (2016).

Article  CAS  Google Scholar 

Riart-Ferrer, X. et al. Metalloradical activation of carbonyl azides for enantioselective radical aziridination. Chem 7, 1120–1134 (2021).

Article  CAS  Google Scholar 

Ma, J.-G. et al. Enantioselective synthesis of pyroglutamic acid esters from glycinate via carbonyl catalysis. Angew. Chem. Int. Ed. 60, 10588–10592 (2021).

Article  CAS  Google Scholar 

Zhang, Y., Qiao, D.-Y., Duan, M., Wang, Y. & Zhu, S.-L. Enantioselective synthesis of α-aminoboronates by NiH-catalysed asymmetric hydroamidation of alkenyl boronates. Nat. Commun. 13, 5630–5637 (2022).

Article  ADS  CAS  Google Scholar 

Cai, Q.-L. et al. Well-defined chiral dinuclear copper complexes in enantioselective propargylic substitution: for a long-standing supposition on binuclear mechanism. Chem 10, 265–282 (2024).

Article  CAS  Google Scholar 

Lauder, K., Toscani, A., Scalacci, N. & Castagnolo, D. Synthesis and reactivity of propargylamines in organic chemistry. Chem. Rev. 117, 14091–14200 (2017).

Article  CAS  Google Scholar 

Rokade, B. V., Barker, J. & Guiry, P. J. Development of and recent advances in asymmetric A3 coupling. Chem. Soc. Rev. 48, 4766–4790 (2019).

Article  CAS  Google Scholar 

Zorba, L. P. & Vougioukalakis, G. C. The ketone-amine-alkyne (KA2) coupling reaction: transition metal-catalyzed synthesis of quaternary propargylamines. Coord. Chem. Rev. 429, 213603 (2021).

Article  CAS  Google Scholar 

Pfeffer, C., Probst, P., Wannenmacher, N., Frey, W. & Peters, R. Direct enantioselective addition of alkynes to imines by a highly efficient palladacycle catalyst. Angew. Chem. Int. Ed. 61, e202206835 (2022).

Article  CAS  Google Scholar 

Morisaki, K. et al. Mechanistic studies and expansion of the substrate scope of direct enantioselective alkynylation of α-ketiminoesters catalyzed by adaptable (phebox)rhodium(III) complexes. J. Am. Chem. Soc. 138, 6194–6230 (2016).

Article  CAS  Google Scholar 

Huang, G.-C., Yang, J. & Zhang, X.-G. Highly enantioselective zinc/BINOL-catalyzed alkynylation of α-ketoimine ester: a new entry to optically active quaternary α-CF3 α-amino acids. Chem. Commun. 47, 5587–5589 (2011).

Article  CAS  Google Scholar 

Hatano, M., Yamashita, K., Mizuno, M., Ito, O. & Ishihara, K. C-selective and diastereoselective alkyl addition to β,γ-alkynyl-imino esters with zinc(II)ate complexes. Angew. Chem. Int. Ed. 54, 2707–2711 (2015).

Article  CAS  Google Scholar 

Trost, B. M., Hung, C.-I. & Scharf, M. J. Direct catalytic asymmetric vinylogous additions of α,β- and β,γ-butenolides to polyfluorinated alkynyl ketimines. Angew. Chem. Int. Ed. 57, 11408–11412 (2018).

Article  CAS  Google Scholar 

Pan, Y.-K. et al. Kinetic resolution of α-tertiary propargylic amines through asymmetric remote aminations of anilines. ACS Catal. 11, 8443–8448 (2021).

Article  CAS  Google Scholar 

Detz, R. J., Delville, M. M. E., Hiemstra, H. & van Maarseveen, J. H. Enantioselective copper-catalyzed propargylic amination. Angew. Chem. Int. Ed. 47, 3777–3780 (2008).

Article  CAS  Google Scholar 

Hattori, G., Matsuzawa, H., Miyake, Y. & Nishibayashi, Y. Copper-catalyzed asymmetric propargylic substitution reactions of propargylic acetates with amines. Angew. Chem. Int. Ed. 47, 3781–3783 (2008).

Article  CAS  Google Scholar 

Miyake, Y., Uemura, S. & Nishibayashi, Y. Catalytic propargylic substitution reactions. ChemCatChem 1, 342–356 (2009).

Article  CAS  Google Scholar 

Detz, R. J., Hiemstra, H. & van Maarseveen, J. H. Catalyzed propargylic substitution. Eur. J. Org. Chem. 63, 6263–6276 (2009).

Article  Google Scholar 

Ding, C.-H. & Hou, X.-L. Catalytic asymmetric propargylation. Chem. Rev. 111, 1914–1937 (2011).

Article  CAS  Google Scholar 

Zhang, D.-Y. & Hu, X.-P. Recent advances in copper-catalyzed propargylic substitution. Tetrahedron Lett. 56, 283–295 (2015).

Article  CAS  Google Scholar 

Hattori, G., Yoshida, A., Miyake, Y. & Nishibayashi, Y. Enantioselective ring-opening reactions of racemic ethynyl epoxides via copper-allenylidene intermediates: efficient approach to chiral β-amino alcohols. J. Org. Chem. 74, 7603–7607 (2009).

Article  CAS  Google Scholar 

Gómez, J. E., Guo, W.-S., Gaspa, S. & Kleij, A. W. Copper-catalyzed synthesis of γ-amino acids featuring quaternary stereocenters. Angew. Chem. Int. Ed. 56, 15035–15038 (2017).

Article  Google Scholar 

Tian, L., Gong, L. & Zhang, X. Copper-catalyzed enantioselective synthesis of β-amino alcohols featuring tetrasubstituted tertiary carbons. Adv. Synth. Catal. 360, 2055–2059 (2018).

Article  CAS  Google Scholar 

Guo, W.-S., Zuo, L.-H., Cui, M.-Y., Yan, B.-W. & Ni, S.-F. Propargylic amination enabled the access to enantioenriched acyclic α-quaternary α-amino ketones. J. Am. Chem. Soc. 143, 7629–7634 (2021).

Article  CAS  Google Scholar 

Liu, T., Ni, S.-F. & Guo, W.-S. Practical asymmetric amine nucleophilic approach for the modular construction of protected α-quaternary amino acids. Chem. Sci. 13, 6806–6812 (2022).

Article  Google Scholar 

Royer, J. Asymmetric Synthesis of Nitrogen Heterocycles (Wiley, 2009).

Phillips, A. M. F. Synthetic Approaches to Nonaromatic Nitrogen Heterocycles (Wiley, 2021).

Hattori, G. et al. Copper-catalyzed enantioselective propargylic amination of propargylic esters with amines: copper-allenylidene complexes as key intermediates. J. Am. Chem. Soc. 132, 10592–10608 (2010).