Emerging catalytic strategies for the stereochemical control of nitrogen centers

Zhongfu Luo

1,2,*,#

Jinhan Ji

1,#

Luhang Yang

Xingxing Wu

1,*

*Correspondence to: Zhongfu Luo, State Key Laboratory of Green Pesticide, Center for R&D of Fine Chemicals of Guizhou University, Huaxi District, Guiyang 550025, Guizhou, China; Key Laboratory of Forest Disaster Warning and Control of Yunnan Province, Southwest Forestry University, Kunming 650224, Yunnan, China. E-mail: luo_zhongfu@swfu.edu.cn
Xingxing Wu, State Key Laboratory of Green Pesticide, Center for R&D of Fine Chemicals of Guizhou University, Huaxi District, Guiyang 550025, Guizhou, China. E-mail: wuxx@gzu.edu.cn

Chiral Chem. 2027;3:202644. 10.70401/cc.2026.0047

Received: September 22, 2026Accepted: November 02, 2026Published: November 03, 2026

This manuscript is made available in its unedited form to allow early access to the reported findings. Further editing will be completed before final publication. As such, the content may include errors, and standard legal disclaimers are applicable.

Abstract

The catalytic asymmetric construction of heteroatom-centered stereogenic units has significantly expanded the scope of modern asymmetric catalysis beyond carbon-centered chirality. In stark contrast to sulfur-, phosphorus-, and silicon-stereogenic frameworks, the enantioselective formation of nitrogen-centered chirality remains one of the most fundamental and unresolved challenges in synthetic catalysis, wherein broadly applicable catalyst-controlled strategies for their asymmetric synthesis are still scarce. This Review provides a comprehensive overview of recent advances in the catalytic asymmetric construction of nitrogen-centered chiral compounds. Emphasis is placed on catalyst design, modes of activation, mechanistic principles, and stereochemical control. The discussion is organized by catalyst class, encompassing transition-metal catalysis, organocatalysis, and bio-catalysis, and further classified by the structural nature of the nitrogen stereogenic unit, including chiral tertiary amines, N(V)-chiral N-oxides, and chiral ammonium ions. This Review aims to establish a unified framework for understanding nitrogen-centered stereochemistry and to stimulate future methodological innovations in this long-standing yet rapidly evolving field.

Keywords

Nitrogen stereogenicity, N-chirality, enantioselective catalysis, organocatalysis, asymmetric metal catalysis

References

1. (a) Doyle AG, Jacobsen EN. Small-molecule H-bond donors in asymmetric catalysis. Chem Rev. 2007;107(12):5713-5743.

[DOI] [PubMed]

(b) List B. Introduction: Organocatalysis. Chem Rev. 2007;107(12):5413-5415.

[DOI]

(c) MacMillan DWC. The advent and development of organocatalysis. Nature. 2008;455(7211):304-308.

[DOI] [PubMed]

(d) Huang S, Zeng Z, Zhang N, Qin W, Lan Y, Yan H. Organocatalytic asymmetric deoxygenation of sulfones to access chiral sulfinyl compounds. Nat Chem. 2023;15(2):185-193.

[DOI]
2. (a) Cui YM, Lin Y, Xu LW. Catalytic synthesis of chiral organoheteroatom compounds of silicon, phosphorus, and sulfur via asymmetric transition metal-catalyzed C-H functionalization. Coord Chem Rev. 2017;330:37-52.

[DOI]

(b) Diesel J, Cramer N. Generation of heteroatom stereocenters by enantioselective C-H functionalization. ACS Catal. 2019;9(10):9164-9177.

[DOI]
3. (a) Wojaczyńska E, Wojaczyński J. Modern stereoselective synthesis of chiral sulfinyl compounds. Chem Rev. 2020;120(10):4578-4611.

[DOI] [PubMed] [PMC]

(b) Zhang X, Ang ECX, Yang Z, Kee CW, Tan CH. Synthesis of chiral sulfinate esters by asymmetric condensation. Nature. 2022;604(7905):298-303.

[DOI] [PubMed] [PMC]

(c) Porey A, Trevino R, Nand S, Fremin SO, Dhakal SK, Dhungana BR, et al. Construction of sulfur stereocentres by asymmetric geminate recasting. Nat Chem. 2025;17(12):1862-1870.

[DOI]

(d) Budeev A, Dong J, Häussinger D, Sparr C. Catalyst control over pentavalent stereocentres. Nat Commun. 2023;14(1):8013.

[DOI] [PubMed] [PMC]

(e) Featherston AL, Kwon Y, Pompeo MM, Engl OD, Leahy DK, Miller SJ. Catalytic asymmetric and stereodivergent oligonucleotide synthesis. Science. 2021;371(6530):702-707.

[DOI] [PubMed] [PMC]

(f) Forbes KC, Jacobsen EN. Enantioselective hydrogen-bond-donor catalysis to access diverse stereogenic-at-P(V) compounds. Science. 2022;376(6598):1230-1236.

[DOI] [PubMed] [PMC]

(g) Wang F, Tan JP, Qian G, Fang S, Liu Z, Li K, et al. Stepwise-controllable catalytic asymmetric Atherton-Todd reaction to access diverse P(V)-stereogenic compounds. Nat Chem. 2026;18(1):23-32.

[DOI] [PubMed]

(h) Xu LW, Li L, Lai GQ, Jiang JX. The recent synthesis and application of silicon-stereogenic silanes: A renewed and significant challenge in asymmetric synthesis. Chem Soc Rev. 2011;40(3):1777-1790.

[DOI] [PubMed]

(i) Ye F, Xu Z, Xu LW. The discovery of multifunctional chiral P ligands for the catalytic construction of quaternary carbon/silicon and multiple stereogenic centers. Acc Chem Res. 2021;54(2):452-470.

[DOI] [PubMed]

(j) Ge Y, Huang X, Ke J, He C. Transition-metal-catalyzed enantioselective C-H silylation. Chem Catal. 2022;2(11):2898-2928.

[DOI]

(k) Zhang G, Zhang Z, Hou M, Cai X, Yang K, Yu P, et al. Construction of boron-stereogenic compounds via enantioselective Cu-catalyzed desymmetric B-H bond insertion reaction. Nat Commun. 2022;13(1):2624.

[DOI] [PubMed] [PMC]

(l) Zu B, Guo Y, He C. Catalytic enantioselective construction of chiroptical boron-stereogenic compounds. J Am Chem Soc. 2021;143(39):16302-16310.

[DOI] [PubMed]
4. (a) Lehn JM. Nitrogen inversion. In: Baldwin JE, Fleming RH, Lehn JM, Tochtermann W, editors. Dynamic stereochemistry. Heidelberg: Springer; 1970. p. 311-377.

[DOI]

(b) Walsh MP, Phelps JM, Lennon ME, Yufit DS, Kitching MO. Enantioselective synthesis of ammonium cations. Nature. 2021;597(7874):70-76.

[DOI]
5. (a) Kaufman TS, Rúveda EA. The quest for quinine: Those who won the battles and those who won the war. Angew Chem Int Ed. 2005;44(6):854-885.

[DOI] [PubMed]

(b) Rao X, Li N, Bai H, Dai C, Wang Z, Tang W. Efficient synthesis of (-)-corynoline by enantioselective palladium-catalyzed α-arylation with sterically hindered substrates. Angew Chem Int Ed. 2018;57(38):12328-12332.

[DOI] [PubMed]

(c) Dolling UH, Davis P, Grabowski EJJ. Efficient catalytic asymmetric alkylations. 1. J Am Chem Soc. 1984;106(2):446-447.

[DOI]

(d) Brown DR, Lygo R, McKenna J, McKenna JM, Hutley BG. The preferred steric course of quaternisation of 1-alkylpiperidines. J Chem Soc, B:. 1967;1184.

[DOI]

(e) Tailor NK. Multifunctional therapeutic potential of corynoline: A benzophenanthridine derived alkaloid. Mini Rev Med Chem. 2026.

[DOI] [PubMed]
6. (a) McVicker RU, O’Boyle NM. Chirality of new drug approvals (2013-2022): Trends and perspectives. J Med Chem. 2024;67(4):2305-2320.

[DOI]

(b) Chen J, Cai L, Zhu Y, Yang G, Gu S. Enantioselective construction of heteroatom stereocenters via N-heterocyclic carbene catalysis. CCS Chem. 2026;8(2):591-606.

[DOI]

(c) Kaplánek R, Havlík M, Dolenský B, Rak J, Džubák P, Konečný P, et al. Synthesis and biological activity evaluation of hydrazone derivatives based on a Tröger’s base skeleton. Bioorg Med Chem. 2015;23(7):1651-1659.

[DOI] [PubMed]
7. (a) Smith O, Popescu MV, Hindson MJ, Paton RS, Burton JW, Smith MD. Control of stereogenic oxygen in a helically chiral oxonium ion. Nature. 2023;615(7952):430-435.

[DOI] [PubMed] [PMC]

(b) Gupta SS, Sharma U. Construction of stereogenic nitrogen compounds: Emerging chemistry. Trends Chem. 2024;6(12):705-708.

[DOI]
8. Hantzsch A, Werner A. Bemerkungen über stereochemisch isomere stickstoffverbindungen. Ber Dtsch Chem Ges. 1890;23(1):1243-1253.

[DOI]
9. Pope WJ, Peachey SJ. CXIV.—Asymmetric optically active nitrogen compounds. Dextro- and lævo-α-benzylphenylallylmethylammonium iodides and bromides. J Chem Soc, Trans. 1899;75:1127-1131.

[DOI]
10. Meisenheimer J. Eine neue art von asymmetrie beim stickstoffatom. Ber Dtsch Chem Ges. 1908;41(3):3966-3976.

[DOI]
11. Prelog V, Wieland P. Über die Spaltung der Tröger’s chen Base in optische Antipoden, ein Beitrag zur Stereochemie des dreiwertigen Stickstoffs. Helvetica Chim Acta. 1944;27(1):1127-1134.

[DOI]
12. (a) Brois SJ. Aziridines. XI. J Am Chem Soc. 1968;90(2):506-508.

[DOI]

(b) Vedejs E, Kendall JT. Aziridine lithiation using lewis acid activation. J Am Chem Soc. 1997;119(29):6941-6942.

[DOI]
13. (a) Mannschreck A, Seitz W. Separation of invertomers (diastereoisomers) of diaziridines. Slow inversion at tervalent nitrogen atoms. Angew Chem Int Ed. 1969;8(3):212-213.

[DOI]

(b) Zhang R, Xu S, Luo Z, Liu Y, Zhang J. Enantiodivergent hydrogenation of exocyclic α, β-unsaturated lactams enabled by switching the N-chirality of iridium catalyst. Angew Chem Int Ed. 2023;62(11):e202213600.

[DOI] [PubMed]

(c) Ravindra S, Irfana Jesin CP, Shabashini A, Nandi GC. Recent advances in the preparations and synthetic applications of oxaziridines and diaziridines. Adv Synth Catal. 2021;363(7):1756-1781.

[DOI]

(d) Williamson KS, Michaelis DJ, Yoon TP. Advances in the chemistry of oxaziridines. Chem Rev. 2014;114(16):8016-8036.

[DOI]

(e) Della Sala G, Lattanzi A. asymmetric catalytic routes to dialkyl peroxides and oxaziridines. ACS Catal. 2014;4(4):1234-1245.

[DOI]
14. (a) Felix D, Eschenmoser A. Slow inversion at pyramidal nitrogen: Isolation of diastereomeric 7-chloro-7-azabicyclo-[4.1.0] heptanes at room temperature. Angew Chem Int Ed. 1968;7(3):224-225.

[DOI]

(b) Rauk A, Allen LC, Mislow K. Pyramidal inversion. Angew Chem Int Ed. 1970;9(6):400-414.

[DOI]
15. (a) Köhler V, Zaitseva S. Pyramidal stereogenic nitrogen centers (SNCs). Synthesis. 2025;57(7):1237-1254.

[DOI]

(b) Kobus M, Friedrich T, Zorn E, Burmeister N, Maison W. Medicinal chemistry of drugs with N-oxide functionalities. J Med Chem. 2024;67(7):5168-5184.

[DOI] [PubMed] [PMC]
16. Emmons WD. The preparation and properties of oxaziranes. J Am Chem Soc. 1957;79(21):5739-5754.

[DOI]
17. (a) Boyd DR, Graham R. Asymmetry in oxaziridines. J Chem Soc C. 1969(20);2648.

[DOI]

(b) Montanari F, Moretti I, Torre G. Asymmetric introduction at trivalent nitrogen. Optically active 2-methyl-3, 3-diphenyloxaziridine, a compound with molecular asymmetry due solely to the nitrogen atom. Chem Commun. 1968(24);1694.

[DOI]
18. Williamson KS, Sawicki JW, Yoon TP. Iron-catalyzed kinetic resolution of N-sulfonyl oxaziridines. Chem Sci. 2014;5(9):3524.

[DOI]
19. (a) Dietrich M, Heinze J, Krieger C, Neugebauer FA. Electrochemical oxidation and structural changes of 5, 6-dihydrobenzo [c] cinnolines. J Am Chem Soc. 1996;118(21):5020-5030.

[DOI]

(b) Laplante SR, D Fader L, Fandrick KR, Fandrick DR, Hucke O, Kemper R, et al. Assessing atropisomer axial chirality in drug discovery and development. J Med Chem. 2011;54(20):7005-7022.

[DOI] [PubMed]
20. Yu T, Cheng S, Luo Y, Li J, Liang Y, Luo S, et al. Immobilizing stereogenic nitrogen center in doubly fused triarylamines through palladium-catalyzed asymmetric C-H activation/seven-membered-ring formation. ACS Catal. 2023;13(14):11292-11299.

[DOI]
21. Sergeyev S. Recent developments in synthetic chemistry, chiral separations, and applications of Tröger’s base analogues. Helv Chim Acta. 2009;92(3):415-444.

[DOI]
22. (a) Harmata M, Kahraman M. Congeners of Troeger’s base as chiral ligands. Tetrahedron: Asymmetry. 2000;11(14):2875-2879.

[DOI]

(b) Shen YM, Zhao MX, Xu J, Shi Y. An amine-promoted aziridination of chalcones. Angew Chem Int Ed. 2006;45(47):8005-8008.

[DOI] [PubMed]

(c) Sigman MS, Jensen DR. Ligand-modulated palladium-catalyzed aerobic alcohol oxidations. Acc Chem Res. 2006;39(3):221-229.

[DOI]

(d) Tatibouët A, Demeunynck M, Andraud C, Collet A, Lhomme J. Synthesis and study of an acridine substituted Tröger’s base: Preferential binding of the (-)—isomer to B-DNA. Chem Commun. 1999;35(2):161-162.

[DOI]

(e) Kimber MC, Try AC, Painter L, Harding MM, Turner P. Synthesis of functionalized chiral carbocyclic cleft molecules complementary to Tröger’s base derivatives. J Org Chem. 2000;65(10):3042-3046.

[DOI]

(f) Kazem-Rostami M. Optically active and photoswitchable Tröger’s base analogs. New J Chem. 2019;43(20):7751-7755.

[DOI]

(g) Antonangelo AR, Hawkins N, Tocci E, Muzzi C, Fuoco A, Carta M. Tröger’s base network polymers of intrinsic microporosity (TB-PIMs) with tunable pore size for heterogeneous catalysis. J Am Chem Soc. 2022;144(34):15581-15594.

[DOI] [PubMed] [PMC]
23. Ma C, Sun Y, Yang J, Guo H, Zhang J. Catalytic asymmetric synthesis of tröger’s base analogues with nitrogen stereocenter. ACS Cent Sci. 2023;9(1):64-71.

[DOI] [PubMed] [PMC]
24. (a) Greenberg A, Molinaro N, Lang M. Structure and dynamics of Troeger’s base and simple derivatives in acidic media. J Org Chem. 1984;49(6):1127-1130.

[DOI]

(b) Trapp O, Trapp G, Kong J, Hahn U, Vögtle F, Schurig V. Probing the stereointegrity of Tröger’s base—A dynamic electrokinetic chromatographic study. Chem Eur J. 2002;8(16):3629-3634.

[DOI] [PubMed]

(c) Lenev DA, Lyssenko KA, Golovanov DG, Buss V, Kostyanovsky RG. Bis-ortho-substitution by methyl groups dramatically increases the racemization barrier of Tröger bases. Chem Eur J. 2006;12(24):6412-6418.

[DOI]
25. (a) Faroughi M, Try AC, Klepetko J, Turner P. Changing the shape of tröger’s base. Tetrahedron Lett. 2007;48(37):6548-6551.

[DOI]

(b) Pereira R, Wolstenhulme J, Sandford G, Claridge TDW, Gouverneur V, Cvengroš J. Synthesis and characterization of a novel N-F reagent derived from the ethano-Tröger’s base: (1)J(FN) coupling constants as a signature for the N-F bond. Chem Commun. 2016;52(8):1606-1609.

[DOI] [PubMed]
26. Guan CY, Lu T, Li Y, Liu CH, Xiao X, Mei GJ. Catalytic enantioselective construction of two N-stereogenic centers of ethano- and propano-Tröger’s bases. Chem Sci. 2025;16(42):19683-19693.

[DOI]
27. (a) Shi BF, Maugel N, Zhang YH, Yu JQ. Pd^II-catalyzed enantioselective activation of C(sp²)-H and C(sp³)-H bonds using monoprotected amino acids as chiral ligands. Angew Chem Int Ed. 2008;47(26):4882-4886.

[DOI]

(b) Saint-Denis TG, Zhu RY, Chen G, Wu QF, Yu JQ. Enantioselective C(sp³)‒H bond activation by chiral transition metal catalysts. Science. 2018;359(6377):eaao4798.

[DOI] [PubMed] [PMC]

(c) Bhat V, Welin ER, Guo X, Stoltz BM. Advances in stereoconvergent catalysis from 2005 to 2015: Transition-metal-mediated stereoablative reactions, dynamic kinetic resolutions, and dynamic kinetic asymmetric transformations. Chem Rev. 2017;117(5):4528-4561.

[DOI] [PubMed] [PMC]

(d) Lainer B, Shuailong L, Mammadova F, Dydio P. A merger of relay catalysis with dynamic kinetic resolution enables enantioselective β-C(sp³)–H arylation of alcohols. Angew Chem Int Ed. 2024;63(35):e202408418.

[DOI]
28. (a) Guan CY, Mei GJ. Harnessing molecular motion for asymmetry-nitrogen inversion as a springboard for stereoselective C-H functionalization. Chiral Chem. 2026;2(2):202605.

[DOI]

(b) Tran DN, Cramer N. Rhodium-catalyzed dynamic kinetic asymmetric transformations of racemic allenes by the [3+2] annulation of aryl ketimines. Angew Chem Int Ed. 2013;52(40):10630-10634.

[DOI]
29. Wu Z, Yi D, Tang J, Meng F, Zhu H, Wu K, et al. Construction of chiral nitrogen stereocenters via enantioselective C–H activation. Chem. 2026;12(1):102730.

[DOI]
30. Jiang YL, Wang BJ, Qian PF, Xu Y, Wang SS, Yao QJ, et al. Efficient construction of nitrogen-stereogenic azepines via Pd(II)-catalyzed enantioselective C-H olefination. ACS Catal. 2026;16(3):2722-2731.

[DOI]
31. (a) Dutartre M, Bayardon J, Jugé S. Applications and stereoselective syntheses of P-chirogenic phosphorus compounds. Chem Soc Rev. 2016;45(20):5771-5794.

[DOI] [PubMed]

(b) Ning X, Zhao T, Zhu Y, Liu B, Yan X, Xia Y. Enantioselective synthesis of axially chiral alkylidenecyclobutanes via palladium-catalyzed N-tosylhydrazone-based carbene coupling. J Am Chem Soc. 2025;147(20):16773-16780.

[DOI] [PubMed]

(c) Zhang JM, Tao SF, Zhao XK, Yang H, Xu G, He ZT. Stereogenic P(V) platform construction via streamlined installation. Sci Bull. 2026;71(8):1957-1967.

[DOI]

(d) Song X, Li X, Wang Z, Zhou L, Chen H, Wang ZX, et al. Nickel-catalyzed H₂-enabled asymmetric olefin isomerization: Direct access to P-stereogenic phospholenes with adjacent stereocenters. Angew Chem Int Ed. 2026;65(40):e6479535.

[DOI]

(e) Xia T, Wu Y, Hu J, Wu X, Qu J, Chen Y. Cobalt-catalyzed asymmetric aza-nozaki-hiyama-kishi (NHK) reaction of α-Imino Esters with alkenyl halides. Angew Chem Int Ed. 2024;63(7):e202316012.

[DOI]
32. Zhang G, Jia J, Du X, Feng B, Yang K, Yu P, et al. Catalytic asymmetric constructions of nitrogen, boron and carbon continuous stereogenic centers. Nat Commun. 2025;16(1):9955.

[DOI] [PubMed] [PMC]
33. (a) Meisenheimer J, Glawe H, Greeske H, Schorning A, Vieweg E. Optisch-aktive aminoxyde. Justus Liebigs Ann Chem. 1926;449(1):188-213.

[DOI]

(b) Meisenheimer J. Optisch aktive aminoxyde. Justus Liebigs Ann Chem. 1922;428(2-3):252-285.

[DOI]

(c) Toda F, Mori K, Stein Z, Goldberg I. Optical resolution of amine N-oxide by diastereoisomeric complex formation with optically active host compound. Tetrahedron Lett. 1989;30(14):1841-1844.

[DOI]

(d) Drabowicz J, Dudziński B, Mikołajczyk M, Colonna S, Gaggero N. Chiral t-butylphenylphosphinothioic acid in NMR analysis of tertiary amine oxides with a stereogenic nitrogen atom. Tetrahedron: Asymmetry. 1997;8(13):2267-2270.

[DOI]
34. Bhadra S, Yamamoto H. Catalytic asymmetric synthesis of N-chiral amine oxides. Angew Chem Int Ed. 2016;55(42):13043-13046.

[DOI]
35. Wu W, Ang ECX, Xu X, Wang Q, Wang H, Lee R, et al. Asymmetric N-oxidation catalyzed by bisguanidinium dinuclear oxodiperoxomolybdosulfate. Nat Commun. 2024;15:7317.

[DOI]
36. (a) Li LM, Yang T, Liu Y, Liu J, Li MH, Wang YT, et al. Calophyline A, a new rearranged monoterpenoid indole alkaloid from Winchia calophylla. Org Lett. 2012;14(13):3450-3453.

[DOI] [PubMed]

(b) Kobylecki RJ, Lane AC, Smith CF, Wakelin LP, Cruse WB, Egert E, et al. N-Methylnalorphine: Definition of N-allyl conformation for antagonism at the opiate receptor. J Med Chem. 1982;25(11):1278-1280.

[DOI] [PubMed]

(c) Faheem , Karan Kumar B, Venkata Gowri Chandra Sekhar K, Chander S, Kunjiappan S, Murugesan S. 1, 2, 3, 4-Tetrahydroisoquinoline (THIQ) as privileged scaffold for anticancer de novo drug design. Expert Opin Drug Discov. 2021;16(10):1119-1147.

[DOI]

(d) Genov GR, Douthwaite JL, Lahdenperä ASK, Gibson DC, Phipps RJ. Enantioselective remote C-H activation directed by a chiral cation. Science. 2020;367(6483):1246-1251.

[DOI] [PubMed]

(e) Brown RCD, Keily JF. Asymmetric permanganate-promoted oxidative cyclization of 1,5-dienes by using chiral phase-transfer catalysis. Angew Chem Int Ed. 2001;40(23):4496-4498.

[DOI]

(f) Ohmatsu K, Ito M, Kunieda T, Ooi T. Ion-paired chiral ligands for asymmetric palladium catalysis. Nat. Chem. 2012;4(6):473-477.

[DOI]
37. (a) Cho H, Jeon H, Shin JE, Lee S, Park S, Kim S. Asymmetric synthesis of Cα-substituted prolines through curtin-Hammett-controlled diastereoselective N-alkylation. Chem Eur J. 2019;25(10):2447-2451.

[DOI] [PubMed]

(b) Wu HF, Lin WB, Xia LZ, Luo YG, Chen XZ, Li GY, et al. ‘N-stereogenic quaternary ammonium salts’ from L-amino acids: Synthesis, separation, and absolute configuration. Helv Chim Acta. 2009;92(4):677-688.

[DOI]
38. Zaitseva S, Prescimone A, Köhler V. Enantioselective allylation of stereogenic nitrogen centers. Org Lett. 2023;25(10):1649-1654.

[DOI]
39. (a) Schmitz E. Three-membered rings with two heteroatoms. In: Advances in heterocyclic chemistry. Amsterdam: Elsevier; 1979. p. 63-107.

[DOI]

(b) Schmitz E. In Diaziridines, 3H-Diazirines, Diaziridinones and Diaziridinimines, Small Ring Heterocycles, Vol. 1; Lowowski, W., Ed, Pergamon Press: Oxford, 1983; p 195
40. (a) Kostyanovsky R, Murugan R, Sutharchanadevi M. In Comprehensive Heterocyclic Chemistry II, Vol. 1A; Padwa, A., Ed, Elsevier: Oxford, 1996; p 347

(b) Makhova NN, Shevtsov AV, Petukhova VY. Transformations of diaziridines and their fused analogues induced by electrophilic reagents. Russ Chem Rev. 2011;80(11):1035-1066.

[DOI]
41. Lykke L, Halskov KS, Carlsen BD, Chen VX, Jørgensen KA. Catalytic asymmetric diaziridination. J Am Chem Soc. 2013;135(12):4692-4695.

[DOI] [PubMed]
42. (a) Kawashima I, Imoto H, Ishida M, Furuta H, Yamamoto S, Mitsuishi M, et al. Dibenzoarsepins: Planarization of 8π-electron system in the lowest singlet excited state. Angew Chem Int Ed. 2019;58(34):11686-11690.

[DOI] [PubMed]

(b) Shukla D, Wan P. Evidence for a planar cyclically conjugated 8. pi. J Am Chem Soc. 1993;115(7):2990-2991.

[DOI]

(c) Shibata T, Uno N, Sasaki T, Takano H, Sato T, Kanyiva KS. Ir-catalyzed synthesis of substituted tribenzosilepins by dehydrogenative C-H/Si-H coupling. J Org Chem. 2018;83(7):3426-3432.

[DOI] [PubMed]

(d) Borst MLG, Bulo RE, Winkel CW, Gibney DJ, Ehlers AW, Schakel M, et al. Phosphepines: convenient access to phosphinidene complexes. J Am Chem Soc. 2005;127(16):5800-5801.

[DOI]

(e) Quillian B, Wang Y, Wei P, Wannere CS, Schleyer PR, Robinson GH. Gallepins. Neutral gallium analogues of the tropylium ion: Synthesis, structure, and aromaticity. J Am Chem Soc. 2007;129(44):13380-13381.

[DOI]

(f) Schickedanz K, Radtke J, Bolte M, Lerner HW, Wagner M. Facile route to quadruply annulated borepins. J Am Chem Soc. 2017;139(7):2842-2851.

[DOI] [PubMed]
43. Huang S, Wen H, Tian Y, Wang P, Qin W, Yan H. Organocatalytic enantioselective construction of chiral azepine skeleton bearing multiple-stereogenic elements. Angew Chem Int Ed. 2021;60(39):21486-21493.

[DOI] [PubMed]
44. Li YW, Mo NN, Zhang H, Wu JX, Han TJ, Xiao X, et al. Organocatalytic asymmetric synthesis of Tröger’s bases. Nat Commun. 2025;16(1):6383.

[DOI] [PubMed] [PMC]
45. Brois SJ. Aziridines. XII. J Am Chem Soc. 1968;90(2):508-509.

[DOI]
46. (a) Shtamburg VG, Rudchenko VF, Grinev VM, Dmitrenko AA, Pleshkova AP, Kostyanovskii RG. Reactions of N-chloro-N-alkoxy-tert-alkylamines with isobutylene and methanol. Bull Acad Sci USSR Div Chem Sci. 1991;40(5):951-954.

[DOI]

(b) Rudchenko VF, Kostyanovsky RG. Geminal oxygen–nitrogen–halogen systems. N-Halohydroxylamine derivatives. Russ Chem Rev. 1998;67(3):179-192.

[DOI]
47. (a) Wu S, Chen P, Duan M, Jiang PY, Zhou Q, Xiang SH, et al. Controlling pyramidal nitrogen chirality by asymmetric organocatalysis. Nature. 2025;647(8091):897-905.

[DOI]

(b) Zheng Y, Liao M, Hao GF, Jin LH, Jayawardana BC, Marambe B, et al. Catalytic enantioselective access to N(iii)-stereogenic aziridines via chiral brønsted acid-catalyzed N-Cl bond formation. Chem Commun. 2026;62(52):13220-13224.

[DOI]
48. Zhu C, Das S, Sterling MS, Tsuji N, Léger SJ, Neese F, et al. The asymmetric synthesis of an acyclic N-stereogenic amine. Nature. 2026;649(8097):621-625.

[DOI] [PubMed] [PMC]
49. (a) Qian D, Sun J. Recent progress in asymmetric ion-pairing catalysis with ammonium salts. Chem A Eur J. 2019;25(15):3740-3751.

[DOI]

(b) Hashimoto T, Maruoka K. Recent development and application of chiral phase-transfer catalysts. Chem Rev. 2007;107(12):5656-5682.

[DOI] [PubMed]
50. Zhang S, Yi D, Li GX, Deng Y, Cui X, Tian Y, et al. Biomimetic dynamic kinetic asymmetric N-oxidation with H₂O₂ and O₂. ACS Catal. 2023;13(18):11954-11962.

[DOI]
51. Luo Z, Liao M, Li W, Zhao S, Tang K, Zheng P, et al. Ionic hydrogen bond-assisted catalytic construction of nitrogen stereogenic center via formal desymmetrization of remote diols. Angew Chem. 2024;136(31):e202404979.

[DOI]
52. Bucciarelli M, Forni A, Moretti I, Prati F. Optically active N-chloro-2, 2-bismethoxycarbonylaziridine by enzymatic hydrolysis. Tetrahedron: Asymmetry. 1990;1(1):5-8.

[DOI]
53. Hadley MR, Švajdlenka E, Damani LA, Oldham HG, Tribe J, Camilleri P, et al. Species variability in the stereoselective N-oxidation of pargyline. Chirality. 1994;6(2):91-97.

[DOI] [PubMed]
54. Ottolina G, Bianchi S, Belloni B, Carrea G, Danieli B. First asymmetric oxidation of tertiary amines by cyclohexanone monooxygenase. Tetrahedron Lett. 1999;40(48):8483-8486.

[DOI]
55. Colonna S, Gaggero N, Drabowicz J, Łyżwa P, Mikołajczyk M. The first efficient bovine serum albumin catalyzed asymmetric oxidation of tertiary amines to the corresponding N-oxides via kinetic dynamic resolution. Chem Commun. 1999;35(18):1787-1788.

[DOI]
56. Suzuki I, Kerakawauchi R, Hirokawa T, Takeda K. Enantioselective preparation of N-chirogenic tertiary amine oxides. Tetrahedron Lett. 2007;48(39):6873-6876.

[DOI]

Copyright

© The Author(s) 2026. This is an Open Access article licensed under a Creative Commons Attribution 4.0 International License (https://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, sharing, adaptation, distribution and reproduction in any medium or format, for any purpose, even commercially, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made.

Publisher’s Note

Science Exploration remains a neutral stance on jurisdictional claims in published maps and institutional affiliations. The views expressed in this article are solely those of the author(s) and do not reflect the opinions of the Editors or the publisher.

Share And Cite

Science Exploration Style

Luo Z, Ji J, Yang L, Wu X. Emerging catalytic strategies for the stereochemical control of nitrogen centers. Chiral Chem. 2027;3:202644. https://doi.org/10.70401/cc.2026.0047