{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,2]],"date-time":"2026-09-02T22:46:05Z","timestamp":1788389165901,"version":"build-2803163510"},"reference-count":47,"publisher":"MDPI AG","issue":"14","license":[{"start":{"date-parts":[[2025,7,10]],"date-time":"2025-07-10T00:00:00Z","timestamp":1752105600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"National Science Foundation Major Research Instrumentation program","award":["DMR-2117502"],"award-info":[{"award-number":["DMR-2117502"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>The reaction of either the L (2S3R) or D (2R3S) enantiomers of H2N-C*H(R)CO2\u2212 (R = -C*H(OH)CH3 or -C*H(OH)CH(CH3)2) and the L (2S) or D (2R) enantiomers of H2N-C*H(C(CH3)2OH)CO2\u2212 with imidazole-4-carboxaldehyde and nickel(II) acetate in methanol yields a single stereoisomer of an oxazolidine. There is retention of chirality on ring positions 4 and 5 (if C\u03b2 is chiral) of the oxazolidine, C\u03b1 and C\u03b2 of the parent amino acid, and transfer of chirality to the newly generated stereogenic centers, ring positions 3, the amino acid nitrogen atom, NAA, and 2, the aldehyde carbon atom, Cald. Specifically, when C\u03b1 has an S configuration, both NAA and Cald are formed as R. Likewise, a C\u03b1 which is R results in both NAA and Cald being formed as S. For example, the reaction of L threonine (C\u03b1 is S and C\u03b2 is R) with 4-imidazolecarboxaldehyde in the presence of nickel(II) gives the facial \u039b NiL2, where L is (2R, 3R, 4S, 5R) 4-carboxylato-5-methyl-2-(4-imidazolyl)-1,3-oxazolidine. The same reaction with D threonine produces the enantiomeric \u0394 complex of (2S, 3S, 4R, 5S) 4-carboxylato-5-methyl-2-(4-imidazoyl)-1,3-oxazolidine. The high stereospecificity is thought to be based on the fused three-ring structure of the characterized nickel complexes in which the hydrogen atoms of C\u03b1, NAA, and Cald must be cis to one another. Identical reactions occur with 2-pyridine carboxaldehyde and LT or DT. In contrast, the reactions of L allo threonine (2S3S) and the primary alcohols, L or D serine, give the conventional meridionally coordinated aldimine product.<\/jats:p>","DOI":"10.3390\/molecules30142913","type":"journal-article","created":{"date-parts":[[2025,7,10]],"date-time":"2025-07-10T15:36:58Z","timestamp":1752161818000},"page":"2913","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["Chirality Transfer and Oxazolidine Formation in Reaction of L and D Enantiomers of \u03b2-Hydroxy Amino Acids with Nitrogenous Carboxaldehydes and Nickel(II)"],"prefix":"10.3390","volume":"30","author":[{"given":"Cynthia T.","family":"Brewer","sequence":"first","affiliation":[{"name":"Department of Chemistry, Catholic University, Washington, DC 20064, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Greg","family":"Brewer","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Catholic University, Washington, DC 20064, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2770-7076","authenticated-orcid":false,"given":"Raymond J.","family":"Butcher","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Howard University, Washington, DC 20059, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2025,7,10]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"8773","DOI":"10.1039\/D2SC02908A","article-title":"Chiral oxazolidines acting as transientlhydroxy-alkyl-functionalized N-heterocyclic carbenes: An efficient route to gold and copper complexes for asymmetric catalysis","volume":"13","author":"Zhang","year":"2022","journal-title":"Chem. Sci."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"3339","DOI":"10.1039\/c0cc04629a","article-title":"Asymmetric catalysis with chiral oxazolidine ligands","volume":"47","author":"Wolf","year":"2011","journal-title":"Chem. Commun."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"6156","DOI":"10.1039\/C7DT04634K","article-title":"Transition metal complexes of a versatile polyalkoxy oxazolidine-based ligand derived from in situ cyclization","volume":"47","author":"Saleem","year":"2018","journal-title":"Dalton Trans."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"10233","DOI":"10.1039\/c3dt50884f","article-title":"Ternary copper(II)-polypyridyl enantiomers: Aldol-type condensation, characterization, DNA-binding recognition, BSA-binding and anticancer property","volume":"42","author":"Ng","year":"2013","journal-title":"Dalton Trans."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"4987","DOI":"10.1039\/C9DT00506D","article-title":"Enantiomeric pairs of ternary copper(ii) complexes and their aldol-type condensation products: Synthesis, characterization, and anticancer and epigenetic properties","volume":"48","author":"Lee","year":"2019","journal-title":"Dalton Trans."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"8695","DOI":"10.1021\/ic900643h","article-title":"Metal-Assisted Oxazolidine\/Oxazine Ring Formation in Dinuclear Zinc(II) Complexes: Synthesis, Structural Aspects, and Bioactivity","volume":"48","author":"Bannerjee","year":"2009","journal-title":"Inorg. Chem."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"122075","DOI":"10.1016\/j.ica.2024.122075","article-title":"Synthesis and characterization of catalytic active oxazolidine\/Schiff complexes using 2-quinoline formaldehyde and tris-base for carbon dioxide chemical fixation","volume":"568","author":"Tuo","year":"2024","journal-title":"Inorg. Chim. Acta"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"12993","DOI":"10.1021\/acs.energyfuels.1c01036","article-title":"Oxazolidine-Based H2S and Mercaptan Scavengers: Uncovering the Myths","volume":"35","author":"Wylde","year":"2021","journal-title":"Energy Fuels"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"293","DOI":"10.1016\/j.fuel.2012.12.071","article-title":"Development of oxazolidines derived from polyisobutylene succinimides as multifunctional stabilizers of asphaltenes in oil industry","volume":"110","author":"Beltran","year":"2013","journal-title":"Fuel"},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"2089","DOI":"10.1021\/cg300096n","article-title":"Polynuclear Complexes of Ligands Containing in Situ Formed Oxazinane and Oxazolidine Rings with Appended Alkoxyl and Phenol Groups","volume":"12","author":"Ding","year":"2012","journal-title":"Cryst. Growth Des."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"9167","DOI":"10.1039\/C5CE01818H","article-title":"A series of tetranuclear lanthanide compounds constructed by in situ polydentate ligands: Synthesis, structure, and SMM behaviour of the Dy4 compound","volume":"17","author":"Lin","year":"2015","journal-title":"CrystEngComm"},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"1643","DOI":"10.1021\/acs.accounts.8b00151","article-title":"Serine\/Threonine Ligation: Origin, Mechanistic Aspects, and Applications","volume":"51","author":"Liu","year":"2018","journal-title":"Acc. Chem. Res."},{"key":"ref_13","doi-asserted-by":"crossref","unstructured":"Wong, C., Li, T., Lam, H., Zhang, Y., and Li, X. (2014). Realizing serine\/threonine ligation: Scope and limitations and mechanistic implication thereof. Front. Chem., 2.","DOI":"10.3389\/fchem.2014.00028"},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"6657","DOI":"10.1073\/pnas.1221012110","article-title":"Protein chemical synthesis by serine and threonine ligation","volume":"110","author":"Zhang","year":"2013","journal-title":"Proc. Natl. Acad. Sci. USA"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"108","DOI":"10.1016\/j.cbpa.2014.09.023","article-title":"Serine\/threonine ligation for the chemical synthesis of proteins","volume":"22","author":"Lee","year":"2014","journal-title":"Curr. Opin. Chem. Biol."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"2251","DOI":"10.1016\/0040-4020(77)80079-3","article-title":"A simple stereochemical model of pyridoxal-dependent aldolase: Asymmetric conversions of the amino acid fragment in chiral complexes of potassium \u0245 and \u0394 bis-\/n-salicylideneaminoacidato\/cobaltate(III)","volume":"33","author":"Belokon","year":"1977","journal-title":"Tetrahedron"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"281","DOI":"10.1016\/j.inoche.2017.10.025","article-title":"A pair of enantiomeric trinuclear nickel (II) clusters based on chiral Schiff-base: Synthesis, structures, circular dichroism and magnetic properties","volume":"86","author":"Liu","year":"2017","journal-title":"Inorg. Chem. Commun."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"7083","DOI":"10.1021\/ic0602953","article-title":"Interaction of Vanadyl (VO2+) with Ligands Containing Serine, Tyrosine, and Threonine","volume":"45","author":"Ebel","year":"2006","journal-title":"Inorg. Chem."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"421","DOI":"10.1016\/j.poly.2014.06.052","article-title":"X-ray structure analysis, electronic and vibrational circular dichroism of chiral-at-metal dioxidovanadium(V) complexes with amino acids derived Schiff base ligands","volume":"81","author":"Krivosudsky","year":"2014","journal-title":"Polyhedron"},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"2295","DOI":"10.1016\/j.poly.2006.01.032","article-title":"Different ways of interaction between binary copper(II)-Schiff bases (Cu\u2013N-salicylideneserinato) and pyrimidine derivatives","volume":"25","author":"Fiol","year":"2006","journal-title":"Polyhedron"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"5781","DOI":"10.1039\/C4OB00555D","article-title":"Electrophilicity and nucleophilicity of commonly used aldehydes","volume":"12","author":"Pratihar","year":"2014","journal-title":"Org. Biomol. Chem."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"7309","DOI":"10.1021\/jo9824908","article-title":"3-Pyridinecarboxaldehyde: A Model System for Superelectrophilic Activation and the Observation of a Diprotonated Electrophile","volume":"64","author":"Klumpp","year":"1999","journal-title":"J. Org. Chem."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"126","DOI":"10.1038\/s42004-019-0224-2","article-title":"How formaldehyde reacts with amino acids","volume":"2","author":"Kamps","year":"2019","journal-title":"Commun. Chem."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"25","DOI":"10.1016\/S0020-1693(00)82990-4","article-title":"Synthesis and structural studies of some metal(II) complexes of 5-methyloxazolidine-4-carboxylic acid","volume":"183","author":"Teo","year":"1991","journal-title":"Inorg. Chim. Acta"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"3361","DOI":"10.1039\/B202955C","article-title":"Reactions of a series of bis(\u03b1 amino acidato) copper(II) complexes with formaldehyde and benzamide: Aldol type condensation versus Mannich aminomethylation","volume":"17","author":"Ng","year":"2002","journal-title":"J. Chem. Soc. Dalton Trans."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"563","DOI":"10.1007\/s11243-016-0053-4","article-title":"Rac-aqua(4-methyl-oxazolidine-4-carboxylato)(nitrato)(1,10-phenanthroline)copper(II), the aldol condensation product of formaldehyde with the D- and L-(alaninato)aqua(1,10-phenanthroline)copper(II) nitrate","volume":"41","author":"Ng","year":"2016","journal-title":"Transit. Met. Chem."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"171","DOI":"10.1038\/s42004-021-00614-y","article-title":"Open questions on the transfer of chirality","volume":"4","author":"Reid","year":"2021","journal-title":"Commun. Chem."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"100161","DOI":"10.1016\/j.giant.2023.100161","article-title":"Preparation of chiral polymers: Precise chirality transfer from natural species to achiral artificial polymers","volume":"14","author":"Miao","year":"2023","journal-title":"Giant"},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"830","DOI":"10.1039\/b806203j","article-title":"Chiral transfer in coordination complexes: Towards molecular materials","volume":"38","author":"Crassous","year":"2009","journal-title":"Chem. Soc. Rev."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"4176","DOI":"10.1021\/acs.cgd.0c00466","article-title":"Chiral oxazolidine complexes derived from phenolic Schiff bases","volume":"20","author":"Mayans","year":"2020","journal-title":"Cryst. Growth Des."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"349","DOI":"10.1134\/S1070328412050119","article-title":"Synthesis and Crystal Structure of a New Nickel(II) Coordination Polymer Based on Schiff Base","volume":"38","author":"Zhang","year":"2012","journal-title":"Russ. Coord. Chem."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"381","DOI":"10.3390\/inorganics11100381","article-title":"Formation of Ketimines from Aldimines in Schiff Base Condensation of Amino Acids and Imidazole-2-Carboxaldehydes: Tautomerization of Schiff Bases of Amino Acids Resulting in the Loss of Stereogenic Center","volume":"11","author":"Brewer","year":"2023","journal-title":"Inorganics"},{"key":"ref_33","doi-asserted-by":"crossref","unstructured":"Brewer, G., Brewer, C., Butcher, R., and Zavalij, P. (2024). Selective Generation of Aldimine and Ketimine Tautomers of the Schiff Base Condensates of Amino Acids with Imidazole Aldehydes or of Imidazole Methanamines with Pyruvates\u2014Isomeric Control with 2- vs. 4-Substituted Imidazoles. Molecules, 29.","DOI":"10.3390\/molecules29061324"},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"2984","DOI":"10.1021\/ic2022984","article-title":"Iminopyridine complexes of manganese, rhenium and molybdenum derived from amino ester (L)-methylserine, and peptides Gly-Gly, GlyVal, and Gly-Gly-Gly. Self-assembly of the peptide chains","volume":"51","author":"Alvarez","year":"2012","journal-title":"Inorg. Chem."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"214051","DOI":"10.1016\/j.ccr.2021.214051","article-title":"Inorganic stereochemistry: Geometric isomerism in bis-tridentate ligand complexes","volume":"445","author":"Juraj","year":"2021","journal-title":"Coord. Chem. Rev."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"59","DOI":"10.1016\/j.ica.2014.04.006","article-title":"Synthesis, supramolecular assemblies and luminescence of nickel (II) complexes based on a series of N-(2-pyridylmethyl) amino acid derivatives","volume":"418","author":"Zhang","year":"2014","journal-title":"Inorg. Chim. Acta"},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"2220","DOI":"10.1016\/j.poly.2010.04.022","article-title":"Chiral heterocyclic ligands XVI: Synthesis and crystal structures of four metal complexes of a tridentate, biheterocyclic ligand derived from l-cysteine","volume":"29","author":"Lewis","year":"2010","journal-title":"Polyhedron"},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"296","DOI":"10.1039\/P29790000296","article-title":"Crystal and molecular structural studies of (\u00b1) and meso-bivalvane","volume":"3","author":"Clardy","year":"1979","journal-title":"J. Chem. Soc. Perkin Trans. 2"},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"11410","DOI":"10.1021\/acs.inorgchem.2c01738","article-title":"Toward Coordination Cages with Hybrid Chirality: Amino Acid-Induced Chirality on Metal Centers","volume":"61","author":"Grajda","year":"2022","journal-title":"Inorg. Chem."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"512","DOI":"10.1039\/D0MA00125B","article-title":"Chirality control of inorganic materials and metals by peptides or amino acids","volume":"1","author":"Kim","year":"2020","journal-title":"Mater. Adv."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"131931","DOI":"10.1016\/j.molstruc.2021.131931","article-title":"Structure co-ordination of solitary amino acids as ligands in metal-organic frameworks (MOFs): A Comprehensive Review","volume":"1251","author":"Subramaniyam","year":"2022","journal-title":"J. Mol. Struct."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"4633","DOI":"10.1021\/cg3008443","article-title":"Variable Water Adsorption in Amino Acid Derivative Based Homochiral Metal Organic Frameworks","volume":"12","author":"Kundu","year":"2012","journal-title":"Cryst. Growth Des."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"5672","DOI":"10.1039\/C4DT03643C","article-title":"Controlling the self-assembly of homochiral coordination architectures of CuII by substitution in amino acid based ligands: Synthesis, crystal structures and physicochemical properties","volume":"44","author":"Kumar","year":"2015","journal-title":"Dalton Trans."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"36","DOI":"10.1016\/j.jorganchem.2013.02.021","article-title":"Synthesis and structural studies of diorganotin(IV) compounds derived from (E)-3-hydroxy-2-((2-hydroxybenzylidene)amino)propanoate and (E)-3-hydroxy-2-((1-(2-hydroxyphenyl)ethylidene)amino)propanoate","volume":"733","author":"Baul","year":"2013","journal-title":"J. Organomet. Chem."},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"467","DOI":"10.1107\/S0108767390000277","article-title":"Phase annealing in SHELX-90: Direct methods for larger structures","volume":"A46","author":"Sheldrick","year":"1990","journal-title":"Acta Crystallogr."},{"key":"ref_46","unstructured":"Sheldrick, G.M. (1997). SHELXL-97: Program for Crystal Structure Refinement, ScienceOpen, Inc."},{"key":"ref_47","unstructured":"Sheldrick, G.M. (1998). SHELXL-97: FORTRAN Program for Crystal Structure Analysis, Gottingen University, Institute Fr Anorganisheche Chemie der Universitat."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/30\/14\/2913\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,9]],"date-time":"2025-10-09T18:07:52Z","timestamp":1760033272000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/30\/14\/2913"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2025,7,10]]},"references-count":47,"journal-issue":{"issue":"14","published-online":{"date-parts":[[2025,7]]}},"alternative-id":["molecules30142913"],"URL":"https:\/\/doi.org\/10.3390\/molecules30142913","relation":{},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2025,7,10]]}}}