{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,28]],"date-time":"2026-09-28T19:02:55Z","timestamp":1790622175388,"version":"4.1.0"},"reference-count":24,"publisher":"American Chemical Society (ACS)","issue":"37","license":[{"start":{"date-parts":[[2026,9,10]],"date-time":"2026-09-10T00:00:00Z","timestamp":1788998400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100013043","name":"Ariel University","doi-asserted-by":"publisher","id":[{"id":"10.13039\/501100013043","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,9,22]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>Asymmetric C\u2013H bond functionalization employing CpXM(III) has gained significant attention in organic synthesis transformations. In this work, the first comprehensive DFT investigation has been performed to gain a better understanding of the origin of enantioselectivity and regioselectivity of Co-catalyzed asymmetric [4+1] annulation of N-chlorobenzamide with cyclopropenes. Our DFT calculations indicate that, although the microkinetic model failed to predict the trans-endo\/cis-endo product ratio, the ratio is within the typical intrinsic error margins of DFT calculations. This thorough DFT analysis is a key to advancing the rational design of enantioselective C\u2013H functionalization transformations with chiral CpXM(III) catalysts.<\/jats:p>","DOI":"10.1021\/acsomega.6c01239","type":"journal-article","created":{"date-parts":[[2026,9,10]],"date-time":"2026-09-10T15:01:24Z","timestamp":1789052484000},"page":"55012-55019","source":"Crossref","is-referenced-by-count":0,"title":["Enantioselective [4+1] Annulation of Benzamide with\nCyclopropene via Chiral CpXCo(III) Catalysis: A DFT Perspective"],"prefix":"10.1021","volume":"11","author":[{"given":"Bat-El","family":"Oded","sequence":"first","affiliation":[{"name":"Ariel University , , ,","place":["Ariel, Israel, 4070000"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3562-0141","authenticated-orcid":true,"given":"Haya","family":"Kornweitz","sequence":"additional","affiliation":[{"name":"Ariel University , , ,","place":["Ariel, Israel, 4070000"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,9,10]]},"reference":[{"issue":"23","key":"2026092814063918800_cit1","doi-asserted-by":"publisher","first-page":"13748","DOI":"10.1021\/acscatal.0c03743","article-title":"Transition Metal Catalyzed\nEnantioselective C(sp2)\u2013H Bond Functionalization","volume":"10","author":"Achar","year":"2020","journal-title":"ACS Catal."},{"issue":"33","key":"2026092814063918800_cit2","doi-asserted-by":"publisher","first-page":"7346","DOI":"10.1002\/chem.201905417","article-title":"Diverse Approaches for Enantioselective\nC\u2013H Functionalization Reactions Using Group 9 CpxMIII Catalysts","volume":"26","author":"Yoshino","year":"2020","journal-title":"Chem. \u2013 A\nEur. J."},{"issue":"7","key":"2026092814063918800_cit3","doi-asserted-by":"publisher","first-page":"3457","DOI":"10.1039\/D3CS00762F","article-title":"Recent Advances in Rh(I)-Catalyzed\nEnantioselective C\u2013H Functionalization","volume":"53","author":"Zhang","year":"2024","journal-title":"Chem. Soc. Rev."},{"issue":"24","key":"2026092814063918800_cit4","doi-asserted-by":"publisher","first-page":"13198","DOI":"10.1002\/anie.202008166","article-title":"Chiral Cyclopentadienyl\nLigands: Design, Syntheses, and Applications in Asymmetric Catalysis","volume":"60","author":"Mas-Rosello\u0301","year":"2021","journal-title":"Angew. Chem. Int. Ed."},{"issue":"5","key":"2026092814063918800_cit5","doi-asserted-by":"publisher","first-page":"1308","DOI":"10.1021\/acs.accounts.5b00092","article-title":"Chiral Cyclopentadienyls: Enabling Ligands for Asymmetric\nRh(III)-Catalyzed C\u2013H Functionalizations","volume":"48","author":"Ye","year":"2015","journal-title":"Acc. Chem. Res."},{"issue":"50","key":"2026092814063918800_cit6","doi-asserted-by":"publisher","first-page":"34786","DOI":"10.1021\/jacs.4c13279","article-title":"Enantiospecific Synthesis\nof Planar Chiral Rhodium and Iridium Cyclopentadienyl Complexes: Enabling\nStreamlined and Computer-Guided Access to Highly Selective Catalysts\nfor Asymmetric C\u2013H Functionalizations","volume":"146","author":"Ye","year":"2024","journal-title":"J. Am. Chem. Soc."},{"issue":"7","key":"2026092814063918800_cit7","doi-asserted-by":"publisher","first-page":"1643","DOI":"10.1039\/D3QO00038A","article-title":"Mechanism\nof Co(III)-Catalyzed Annulation of N-Chlorobenzamide with Styrene\nand Origin of Cyclopentadienyl Ligand-Controlled Enantioselectivity","volume":"10","author":"Gao","year":"2023","journal-title":"Org. Chem. Front."},{"issue":"6106","key":"2026092814063918800_cit8","doi-asserted-by":"publisher","first-page":"504","DOI":"10.1126\/science.1226938","article-title":"Chiral Cyclopentadienyl Ligands as Stereocontrolling\nElement in Asymmetric C\u2013H Functionalization","volume":"338","author":"Ye","year":"2012","journal-title":"Science"},{"issue":"18","key":"2026092814063918800_cit9","doi-asserted-by":"publisher","first-page":"15041","DOI":"10.1021\/jacs.4c16953","article-title":"Enantioselective Cobalt(III)-Catalyzed\n[4 + 1] Annulation of Benzamides: Cyclopropenes as One-Carbon Synthons","volume":"147","author":"Verdhi","year":"2025","journal-title":"J. Am. Chem. Soc."},{"issue":"1","key":"2026092814063918800_cit10","doi-asserted-by":"publisher","first-page":"262","DOI":"10.1021\/acscatal.5b01891","article-title":"A DFT Study on Rh-Catalyzed Asymmetric\nDearomatization of 2-Naphthols Initiated with C\u2013H Activation:\nA Refined Reaction Mechanism and Origins of Multiple Selectivity","volume":"6","author":"Zheng","year":"2016","journal-title":"ACS Catal."},{"issue":"4","key":"2026092814063918800_cit11","doi-asserted-by":"publisher","first-page":"3453","DOI":"10.1021\/acscatal.5c07589","article-title":"Enantioselective\nOlefin 1,2-Arylamination Catalyzed by a Planar Chiral Indenyl-Rhodium(III)\nComplex","volume":"16","author":"Gross","year":"2026","journal-title":"ACS Catal."},{"key":"2026092814063918800_cit12","unstructured":"Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Petersson, G. A.; Nakatsuji, H.; et al.; Gaussian 16, Revision C.01; Gaussian, Inc.: Walliningford CT, 2016."},{"issue":"1","key":"2026092814063918800_cit13","doi-asserted-by":"publisher","first-page":"215","DOI":"10.1007\/s00214-007-0310-x","article-title":"The M06 Suite of Density Functionals for Main Group\nThermochemistry, Thermochemical Kinetics, Noncovalent Interactions,\nExcited States, and Transition Elements: Two New Functionals and Systematic\nTesting of Four M06-Class Functionals and 12 Other Functionals","volume":"120","author":"Zhao","year":"2008","journal-title":"Theor. Chem. Acc."},{"issue":"10","key":"2026092814063918800_cit14","doi-asserted-by":"publisher","first-page":"5639","DOI":"10.1063\/1.438980","article-title":"Contracted Gaussian Basis Sets for Molecular Calculations.\nI. Second Row Atoms, Z=11\u201318","volume":"72","author":"McLean","year":"1980","journal-title":"J. Chem.\nPhys."},{"key":"2026092814063918800_cit15","volume-title":"Methods of Electronic\nStructure Theory","author":"Dunning T","year":"1977"},{"issue":"15","key":"2026092814063918800_cit16","doi-asserted-by":"publisher","first-page":"154104","DOI":"10.1063\/1.3382344","article-title":"A Consistent and Accurate\nAb Initio Parametrization of Density Functional Dispersion Correction\n(DFT-D) for the 94 Elements H-Pu","volume":"132","author":"Grimme","year":"2010","journal-title":"J. Chem. Phys."},{"issue":"18","key":"2026092814063918800_cit17","doi-asserted-by":"publisher","first-page":"6378","DOI":"10.1021\/jp810292n","article-title":"Universal Solvation Model Based on\nSolute Electron Density and on a Continuum Model of the Solvent Defined\nby the Bulk Dielectric Constant and Atomic Surface Tensions","volume":"113","author":"Marenich","year":"2009","journal-title":"J. Phys. Chem. B"},{"issue":"13","key":"2026092814063918800_cit18","doi-asserted-by":"publisher","first-page":"130902","DOI":"10.1063\/1.5143207","article-title":"First-Principles\nModeling of Chemistry in Mixed Solvents: Where to Go from Here?","volume":"152","author":"Maldonado","year":"2020","journal-title":"J. Chem. Phys."},{"issue":"14","key":"2026092814063918800_cit19","doi-asserted-by":"publisher","first-page":"7169","DOI":"10.1039\/C9CP06869D","article-title":"Automated Exploration of the Low-Energy\nChemical Space with Fast Quantum Chemical Methods","volume":"22","author":"Pracht","year":"2020","journal-title":"Phys. Chem. Chem. Phys."},{"issue":"15","key":"2026092814063918800_cit20","doi-asserted-by":"publisher","first-page":"4483","DOI":"10.1021\/acs.jcim.3c00271","article-title":"The NCIWEB\nServer: A Novel Implementation of the Noncovalent Interactions Index\nfor Biomolecular Systems","volume":"63","author":"Novoa","year":"2023","journal-title":"J. Chem. Inf. Model."},{"issue":"15","key":"2026092814063918800_cit21","doi-asserted-by":"publisher","first-page":"6975","DOI":"10.1021\/acs.chemrev.7b00617","article-title":"Spin-Vibronic Mechanism\nfor Intersystem Crossing","volume":"118","author":"Penfold","year":"2018","journal-title":"Chem. Rev."},{"issue":"13","key":"2026092814063918800_cit22","doi-asserted-by":"publisher","first-page":"134106","DOI":"10.1063\/5.0102857","article-title":"Rapid Calculation of Internal Conversion and Intersystem\nCrossing Rate for Organic Materials Discovery","volume":"157","author":"Shi","year":"2022","journal-title":"J. Chem. Phys."},{"issue":"28","key":"2026092814063918800_cit23","doi-asserted-by":"publisher","first-page":"8860","DOI":"10.1021\/ja072208r","article-title":"Cobalt-Catalyzed\nCyclotrimerization of Alkynes: The Answer to the Puzzle of Parallel\nReaction Pathways","volume":"129","author":"Agenet","year":"2007","journal-title":"J. Am. Chem. Soc."},{"issue":"26","key":"2026092814063918800_cit24","doi-asserted-by":"publisher","first-page":"8509","DOI":"10.1021\/ja060756j","article-title":"Cobalt-Mediated\nCyclic and Linear 2: 1 Cooligomerization of Alkynes with Alkenes:\nA DFT Study","volume":"128","author":"Gandon","year":"2006","journal-title":"J. Am. Chem. Soc."}],"container-title":["ACS Omega"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/acsomega.6c01239","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/acsodf\/article-pdf\/11\/37\/55012\/68473982\/acsomega.6c01239.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/acsodf\/article-pdf\/11\/37\/55012\/68473982\/acsomega.6c01239.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,9,28]],"date-time":"2026-09-28T18:29:14Z","timestamp":1790620154000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/acsodf\/article\/11\/37\/55012\/5427807\/Enantioselective-4-1-Annulation-of-Benzamide-with"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,9,10]]},"references-count":24,"journal-issue":{"issue":"37","published-online":{"date-parts":[[2026,9,10]]},"published-print":{"date-parts":[[2026,9,22]]}},"URL":"https:\/\/doi.org\/10.1021\/acsomega.6c01239","relation":{},"ISSN":["2470-1343"],"issn-type":[{"value":"2470-1343","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,9,10]]}}}