{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,21]],"date-time":"2026-10-21T15:53:46Z","timestamp":1792598026763,"version":"4.5.0"},"reference-count":60,"publisher":"American Chemical Society (ACS)","license":[{"start":{"date-parts":[[2026,10,21]],"date-time":"2026-10-21T00:00:00Z","timestamp":1792540800000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-029"},{"start":{"date-parts":[[2026,10,21]],"date-time":"2026-10-21T00:00:00Z","timestamp":1792540800000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-037"},{"start":{"date-parts":[[2026,10,21]],"date-time":"2026-10-21T00:00:00Z","timestamp":1792540800000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-045"}],"funder":[{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["22273051"],"award-info":[{"award-number":["22273051"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"name":"Carbon Neutrality Research Institute","award":["CNIF20240110"],"award-info":[{"award-number":["CNIF20240110"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>Density functional theory calculations were carried out to elucidate the mechanism and the origin of regio- and stereoselectivity in the palladium-catalyzed [6+2] annulation of allenyl benzoxazinanones with terminal allenes. An unconventional oxidative addition\u2013reductive elimination mechanism was revealed. The reaction starts with SN2-type oxidative addition of the substrate to Pd0, followed by decarboxylation to afford a \u03c0-allylpalladium intermediate. Pathway bifurcation leads to competing [6+2] and [4+2] annulations, and the more stable seven-membered palladacycle kinetically favors the [6+2] pathway and inhibits the [4+2] side reaction. Distortion\/interaction analysis indicates that the exclusive Z-selectivity originates from the larger structural distortion of the E-configured transition state. Different from conventional three-center reductive elimination, the reaction proceeds via a zwitterionic-intermediate-mediated nucleophilic coupling pathway, which acts as the rate-limiting step with an overall barrier of 21.3 kcal\/mol. This work rationalizes experimental selectivity and offers theoretical guidance for the design of related Pd-catalyzed annulation reactions.<\/jats:p>","DOI":"10.1021\/acs.joc.6c01402","type":"journal-article","created":{"date-parts":[[2026,10,21]],"date-time":"2026-10-21T15:01:32Z","timestamp":1792594892000},"source":"Crossref","is-referenced-by-count":0,"title":["Mechanism and Origin of Regio- and Stereoselectivity in the Synthesis of Benzazocines via Palladium-Catalyzed [6+2] Annulation of Allenyl Benzoxazinanones with Terminal Allenes"],"prefix":"10.1021","author":[{"ORCID":"https:\/\/orcid.org\/0009-0007-3623-7973","authenticated-orcid":true,"given":"Jinglong","family":"Xin","sequence":"first","affiliation":[{"name":"Shandong University , , ,","place":["Jinan, P. R. China, 250100"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Aili","family":"Feng","sequence":"additional","affiliation":[{"name":"Shandong University , , ,","place":["Jinan, P. R. China, 250100"]},{"name":"Carbon Neutrality Research Institute , , ,","place":["Dongying, P. R. China, 257061"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jihong","family":"Xu","sequence":"additional","affiliation":[{"name":"Carbon Neutrality Research Institute , , ,","place":["Dongying, P. R. China, 257061"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5840-9149","authenticated-orcid":true,"given":"Yanling","family":"Zhao","sequence":"additional","affiliation":[{"name":"Shenzhen Polytechnic University , , ,","place":["Shenzhen, P. R. China, 518055"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6117-4958","authenticated-orcid":true,"given":"Dongju","family":"Zhang","sequence":"additional","affiliation":[{"name":"Shandong University , , ,","place":["Jinan, P. R. China, 250100"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,10,21]]},"reference":[{"key":"2026102111012685000_cit1","doi-asserted-by":"publisher","first-page":"2767","DOI":"10.1016\/0040-4020(69)80020-7","article-title":"The Structure Elucidation of Three Tetrahydroquinolylimidazole Alkaloids from Macrorungia Longistrobus C.B.Cl. (Acanthaceae)","volume":"25","author":"Arndt","year":"1969","journal-title":"Tetrahedron"},{"key":"2026102111012685000_cit2","doi-asserted-by":"publisher","first-page":"11752","DOI":"10.1021\/ja0651815","article-title":"A Convergent and Enantioselective Synthesis of (+)-Amurensinine via Selective C\u2013H and C\u2013C Bond Insertion Reactions","volume":"128","author":"Tambar","year":"2006","journal-title":"J. Am. Chem. Soc."},{"key":"2026102111012685000_cit3","doi-asserted-by":"publisher","first-page":"1777","DOI":"10.1021\/cr050029r","article-title":"Natural Products with Maleic Anhydride Structure: Nonadrides, Tautomycin, Chaetomellic Anhydride, and Other Compounds","volume":"107","author":"Chen","year":"2007","journal-title":"Chem. Rev."},{"key":"2026102111012685000_cit4","doi-asserted-by":"publisher","first-page":"2066","DOI":"10.1021\/jo00033a030","article-title":"Sulpinines A\u2013C and Secopenitrem B: New Antiinsectan Metabolites from the Sclerotia of Aspergillus Sulphureus","volume":"57","author":"Laakso","year":"1992","journal-title":"J. Org. Chem."},{"key":"2026102111012685000_cit5","doi-asserted-by":"publisher","first-page":"838","DOI":"10.1021\/jm020429w","article-title":"Syntheses and Opioid Receptor Binding Affinities of 8-Amino-2,6-methano-3-benzazocines","volume":"46","author":"Wentland","year":"2003","journal-title":"J. Med. Chem."},{"key":"2026102111012685000_cit6","doi-asserted-by":"publisher","first-page":"5200","DOI":"10.1021\/ol202074e","article-title":"Palladium-Catalyzed Approach to Stereodefined Ten-Membered Cycles from 1,5-Bisallenes","volume":"13","author":"Cheng","year":"2011","journal-title":"Org. Lett."},{"key":"2026102111012685000_cit7","volume-title":"Comprehensive Heterocyclic Chemistry IV","author":"Black","year":"2022"},{"key":"2026102111012685000_cit8","doi-asserted-by":"publisher","first-page":"5677","DOI":"10.1016\/j.bmcl.2010.08.024","article-title":"Indoloditerpenes from an Algicolous Isolate of Aspergillus oryzae","volume":"20","author":"Qiao","year":"2010","journal-title":"Bioorg. Med. Chem. Lett."},{"key":"2026102111012685000_cit9","doi-asserted-by":"publisher","first-page":"2275","DOI":"10.1055\/s-2006-949654","article-title":"Sequential Amino-Claisen Rearrangement\/Intramolecular 1,3-Dipolar \u00adCycloaddition\/Reductive Cleavage Approach to the Stereoselective Synthesis of cis-4-Hydroxy-2-aryl-2,3,4,5-tetrahydro-1(1H)-benzazepines","volume":"14","author":"Ayala","year":"2006","journal-title":"Synlett."},{"key":"2026102111012685000_cit10","doi-asserted-by":"publisher","first-page":"266","DOI":"10.1021\/acs.orglett.6b03577","article-title":"Synthesis of Tricyclic Benzazocines by Aza-Prins Reaction","volume":"19","author":"Katamura","year":"2017","journal-title":"Org. Lett."},{"key":"2026102111012685000_cit11","doi-asserted-by":"publisher","first-page":"863","DOI":"10.1055\/s-0029-1218620","article-title":"Synthesis of Azepine- and Azocine-Annulated Heterocycles by Aromatic Aza-Claisen Rearrangement and Ring-Closing Metathesis","volume":"5","author":"Majumdar","year":"2010","journal-title":"Synlett"},{"key":"2026102111012685000_cit12","doi-asserted-by":"publisher","first-page":"5849","DOI":"10.1021\/jo9707085","article-title":"Synthesis and Evaluation of CC-1065 and Duocarmycin Analogs Incorporating the 1,2,3,4,11,11a-Hexahydrocyclopropa[c]Naphtho[2,1-b]Azepin-6-One (CNA) Alkylation Subunit: Structural Features that Govern Reactivity and Reaction Regioselectivity","volume":"62","author":"Boger","year":"1997","journal-title":"J. Org. Chem."},{"key":"2026102111012685000_cit13","doi-asserted-by":"publisher","first-page":"7817","DOI":"10.1002\/anie.201202971","article-title":"One-Pot Approach to Installing Eight-Membered Rings onto Indoles","volume":"51","author":"Zhu","year":"2012","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026102111012685000_cit14","doi-asserted-by":"publisher","first-page":"2549","DOI":"10.1021\/ol0709329","article-title":"Ring-Closing Reaction of Allenic\/Propargylic Anions Generated by Base Treatment of Sulfonylallenes","volume":"9","author":"Kitagaki","year":"2007","journal-title":"Org. Lett."},{"key":"2026102111012685000_cit15","doi-asserted-by":"publisher","first-page":"1208","DOI":"10.1002\/anie.201307391","article-title":"The Witkop Cyclization: A Photoinduced C-H Activation of the Indole System","volume":"53","author":"Gritsch","year":"2014","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026102111012685000_cit16","doi-asserted-by":"publisher","first-page":"5656","DOI":"10.1021\/ja0010507","article-title":"Towards Diversity-Oriented, Stereoselective Syntheses of Biaryl- or Bis(aryl)Metal-Containing Medium Rings","volume":"122","author":"Spring","year":"2000","journal-title":"J. Am. Chem. Soc."},{"key":"2026102111012685000_cit17","doi-asserted-by":"publisher","first-page":"2777","DOI":"10.1016\/0040-4020(94)01064-7","article-title":"Medium Ring Lactones","volume":"51","author":"Rousseau","year":"1995","journal-title":"Tetrahedron"},{"key":"2026102111012685000_cit18","doi-asserted-by":"publisher","first-page":"239","DOI":"10.1021\/cr050045o","article-title":"Total Synthesis of Natural 8- and 9-Membered Lactones: Recent Advancements in Medium-Sized Ring Formation","volume":"107","author":"Shiina","year":"2007","journal-title":"Chem. Rev."},{"key":"2026102111012685000_cit19","doi-asserted-by":"publisher","first-page":"4678","DOI":"10.1021\/ja00275a085","article-title":"Nickel-Catalyzed Intramolecular [4+4]-Cycloadditions: A New Method for the Synthesis of Polycycles Containing Eight-Membered Rings","volume":"108","author":"Wender","year":"1986","journal-title":"J. Am. Chem. Soc."},{"key":"2026102111012685000_cit20","doi-asserted-by":"publisher","first-page":"7815","DOI":"10.1021\/ja001483+","article-title":"Transition Metal-Catalyzed [6+2] Cycloadditions of 2-Vinylcyclobutanones and Alkenes: A New Reaction for the Synthesis of Eight-Membered Rings","volume":"122","author":"Wender","year":"2000","journal-title":"J. Am. Chem. Soc."},{"key":"2026102111012685000_cit21","doi-asserted-by":"publisher","first-page":"2876","DOI":"10.1021\/ja0176301","article-title":"Three-Component Cycloadditions: The First Transition Metal-Catalyzed [5+2+1] Cycloaddition Reactions","volume":"124","author":"Wender","year":"2002","journal-title":"J. Am. Chem. Soc."},{"key":"2026102111012685000_cit22","doi-asserted-by":"publisher","first-page":"8782","DOI":"10.1021\/ja026351q","article-title":"Intermolecular Transition Metal-Catalyzed [4+2+2] Cycloaddition Reactions: A New Approach to the Construction of Eight-Membered Rings","volume":"124","author":"Evans","year":"2002","journal-title":"J. Am. Chem. Soc."},{"key":"2026102111012685000_cit23","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202213676","article-title":"Palladium-Catalyzed [6+2] Double Allene Annulation for Benzazocines Synthesis","volume":"62","author":"Xu","year":"2023","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026102111012685000_cit24","doi-asserted-by":"publisher","first-page":"14694","DOI":"10.1002\/anie.201907375","article-title":"A Mechanistic Analysis of the Palladium-Catalyzed Formation of Branched Allylic Amines Reveals the Origin of the Regio- and Enantioselectivity through a Unique Inner-Sphere Pathway","volume":"58","author":"Hu","year":"2019","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026102111012685000_cit25","doi-asserted-by":"publisher","first-page":"17180","DOI":"10.1021\/ja055968f","article-title":"Palladium Catalyzed Asymmetric Allylic \u03b1-Alkylation of Acyclic Ketones","volume":"127","author":"Trost","year":"2005","journal-title":"J. Am. Chem. Soc."},{"key":"2026102111012685000_cit26","doi-asserted-by":"publisher","first-page":"511","DOI":"10.1016\/S0010-8545(98)00073-3","article-title":"Role of dba in the Reactivity of Palladium(0) Complexes Generated in Situ from Mixtures of Pd(dba)2 and Phosphines","volume":"178\u2013180","author":"Amatore","year":"1998","journal-title":"Coord. Chem. Rev."},{"key":"2026102111012685000_cit27","doi-asserted-by":"publisher","first-page":"999","DOI":"10.1021\/acscatal.9b04666","article-title":"Unraveling the High Activity of Ylide-Functionalized Phosphines in Palladium-Catalyzed Amination Reactions: A Comparative Study with CyJohnPhos and PtBu3","volume":"10","author":"Scharf","year":"2020","journal-title":"ACS Catal."},{"key":"2026102111012685000_cit28","volume-title":"Gaussian 09, Revision B.01","author":"Frisch","year":"2010"},{"key":"2026102111012685000_cit29","doi-asserted-by":"publisher","first-page":"3098","DOI":"10.1103\/PhysRevA.38.3098","article-title":"Density-functional Exchange-energy Approximation with Correct Asymptotic Behavior","volume":"38","author":"Becke","year":"1988","journal-title":"Phys. Rev. A"},{"key":"2026102111012685000_cit30","doi-asserted-by":"publisher","first-page":"785","DOI":"10.1103\/PhysRevB.37.785","article-title":"Development of the Colle-Salvetti Correlation-energy Formula into A Functional of the Electron Density","volume":"37","author":"Lee","year":"1988","journal-title":"Phys. Rev. B"},{"key":"2026102111012685000_cit31","doi-asserted-by":"publisher","DOI":"10.1063\/1.3382344","article-title":"A Consistent and Accurate Ab Initio Parametrization of Density Functional Dispersion Correction (DFT-D) for the 94 Elements H-Pu","volume":"132","author":"Grimme","year":"2010","journal-title":"J. Chem. Phys."},{"key":"2026102111012685000_cit32","doi-asserted-by":"publisher","first-page":"270","DOI":"10.1063\/1.448799","article-title":"Ab Initio Effective Core Potentials for Molecular Calculations. Potentials for the Transition Metal Atoms Sc to Hg","volume":"82","author":"Hay","year":"1985","journal-title":"J. Chem. Phys."},{"key":"2026102111012685000_cit33","doi-asserted-by":"publisher","first-page":"299","DOI":"10.1063\/1.448975","article-title":"Ab Initio Effective Core Potentials for Molecular Calculations. Potentials for Potassium to Gold including the Outermost Core Orbitals","volume":"82","author":"Hay","year":"1985","journal-title":"J. Chem. Phys."},{"key":"2026102111012685000_cit34","doi-asserted-by":"publisher","first-page":"111","DOI":"10.1016\/0009-2614(93)80086-5","article-title":"A Set of f-Polarization Functions for Pseudo-Potential Basis Sets of the Transition Metals Sc-Cu, Y-Ag and La-Au","volume":"208","author":"Ehlers","year":"1993","journal-title":"Chem. Phys. Lett."},{"key":"2026102111012685000_cit35","doi-asserted-by":"publisher","first-page":"281","DOI":"10.1016\/0167-7977(85)90003-6","article-title":"Basis Sets for Molecular Calculations","volume":"2","author":"Huzinaga","year":"1985","journal-title":"Comput. Phys. Rep."},{"key":"2026102111012685000_cit36","doi-asserted-by":"publisher","first-page":"2257","DOI":"10.1063\/1.1677527","article-title":"Self-Consistent Molecular Orbital Methods. XII. Further Extensions of Gaussian-Type Basis Sets for Use in Molecular Orbital Studies of Organic Molecules","volume":"56","author":"Hehre","year":"1972","journal-title":"J. Chem. Phys."},{"key":"2026102111012685000_cit37","doi-asserted-by":"publisher","first-page":"6378","DOI":"10.1021\/jp810292n","article-title":"Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions","volume":"113","author":"Marenich","year":"2009","journal-title":"J. Phys. Chem. B"},{"key":"2026102111012685000_cit38","doi-asserted-by":"publisher","first-page":"4161","DOI":"10.1021\/j100717a029","article-title":"Formulation of the Reaction Coordinate","volume":"74","author":"Fukui","year":"1970","journal-title":"J. Phys. Chem."},{"key":"2026102111012685000_cit39","doi-asserted-by":"publisher","first-page":"363","DOI":"10.1021\/ar00072a001","article-title":"The Path of Chemical Reactions-the IRC Approach","volume":"14","author":"Fukui","year":"1981","journal-title":"Acc. Chem. Res."},{"key":"2026102111012685000_cit40","doi-asserted-by":"publisher","first-page":"123","DOI":"10.1007\/BF01114537","article-title":"Energy-Adjusted ab Initio Pseudopotentials for the Second and Third Row Transition Elements","volume":"77","author":"Andrae","year":"1990","journal-title":"Theor. Chim. Acta"},{"key":"2026102111012685000_cit41","doi-asserted-by":"publisher","first-page":"9709","DOI":"10.1021\/jp802665d","article-title":"Calculation of Solvation Free Energies of Charged Solutes Using Mixed Cluster\/Continuum Models","volume":"112","author":"Bryantsev","year":"2008","journal-title":"J. Phys. Chem. B"},{"key":"2026102111012685000_cit42","doi-asserted-by":"publisher","first-page":"157","DOI":"10.1021\/ar700111a","article-title":"Density Functionals with Broad Applicability in Chemistry","volume":"41","author":"Zhao","year":"2008","journal-title":"Acc. Chem. Res."},{"key":"2026102111012685000_cit43","doi-asserted-by":"publisher","first-page":"735","DOI":"10.1063\/1.449486","article-title":"Natural Population Analysis","volume":"83","author":"Reed","year":"1985","journal-title":"J. Chem. Phys."},{"key":"2026102111012685000_cit44","volume-title":"NBO, version 3.1","author":"Glendening","year":"1995"},{"key":"2026102111012685000_cit45","volume-title":"CYLview, 1.0b","author":"Legault","year":"2009"},{"key":"2026102111012685000_cit46","doi-asserted-by":"publisher","first-page":"2868","DOI":"10.1002\/jcc.26068","article-title":"Exploring Nature and Predicting Strength of Hydrogen Bonds: A Correlation Analysis Between Atoms-in-Molecules Descriptors, Binding Energies, and Energy Components of Symmetry-Adapted Perturbation Theory","volume":"40","author":"Emamian","year":"2019","journal-title":"J. Comput. Chem."},{"key":"2026102111012685000_cit47","doi-asserted-by":"publisher","first-page":"580","DOI":"10.1002\/jcc.22885","article-title":"Multiwfn: A Multifunctional Wavefunction Analyzer","volume":"33","author":"Lu","year":"2012","journal-title":"J. Comput. Chem."},{"key":"2026102111012685000_cit48","doi-asserted-by":"publisher","first-page":"33","DOI":"10.1016\/0263-7855(96)00018-5","article-title":"VMD: Visual Molecular Dynamics","volume":"14","author":"Humphrey","year":"1996","journal-title":"J. Mol. Graph."},{"key":"2026102111012685000_cit49","doi-asserted-by":"publisher","first-page":"14161","DOI":"10.1021\/acscatal.4c03771","article-title":"Interception of Transient anti-Allyl-Ir Species with Cu-Azomethine Ylide: Mechanistic Origins of Z-Selectivity in an Asymmetric Allylation Reaction","volume":"14","author":"Xu","year":"2024","journal-title":"ACS Catal."},{"key":"2026102111012685000_cit50","doi-asserted-by":"publisher","first-page":"2722","DOI":"10.1021\/acscatal.2c00016","article-title":"Computational Insights into Palladium\/Boron-Catalyzed Allylic Substitution of Vinylethylene Carbonates with Water: Outer-Sphere versus Inner-Sphere Pathway and Origins of Regio- and Enantioselectivities","volume":"12","author":"Wu","year":"2022","journal-title":"ACS Catal."},{"key":"2026102111012685000_cit51","doi-asserted-by":"publisher","first-page":"13917","DOI":"10.1021\/jacs.0c06243","article-title":"Reaction Mechanism, Origins of Enantioselectivity, and Reactivity Trends in Asymmetric Allylic Alkylation: A Comprehensive Quantum Mechanics Investigation of a C(sp3)\u2013C(sp3) Cross-Coupling","volume":"142","author":"Cusumano","year":"2020","journal-title":"J. Am. Chem. Soc."},{"key":"2026102111012685000_cit52","doi-asserted-by":"publisher","first-page":"10070","DOI":"10.1002\/anie.201701486","article-title":"Analyzing Reaction Rates with the Distortion\/Interaction-Activation Strain Model","volume":"56","author":"Bickelhaupt","year":"2017","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026102111012685000_cit53","doi-asserted-by":"publisher","first-page":"11150","DOI":"10.1021\/acs.joc.9b01868","article-title":"C\u2013H Activation versus Ring Opening and Inner- versus Outer-Sphere Concerted Metalation\u2013Deprotonation in Rh(III)-Catalyzed Oxidative Coupling of Oxime Ether and Cyclopropanol: A Density Functional Theory Study","volume":"84","author":"Meng","year":"2019","journal-title":"J. Org. Chem."},{"key":"2026102111012685000_cit54","doi-asserted-by":"publisher","first-page":"2594","DOI":"10.1021\/acs.organomet.8b00338","article-title":"Theoretical Mechanistic Study of Nickel(0)\/Lewis Acid Catalyzed Polyfluoroarylcyanation of Alkynes: Origin of Selectivity for C\u2013CN Bond Activation","volume":"37","author":"Ren","year":"2018","journal-title":"Organometallics"},{"key":"2026102111012685000_cit55","doi-asserted-by":"publisher","first-page":"2207","DOI":"10.1021\/jacs.2c09739","article-title":"Revised Mechanism of C(sp3)\u2013C(sp3) Reductive Elimination from Ni(II) with the Assistance of a Z-Type Metalloligand","volume":"145","author":"Zhang","year":"2023","journal-title":"J. Am. Chem. Soc."},{"key":"2026102111012685000_cit56","doi-asserted-by":"publisher","first-page":"833","DOI":"10.1021\/acs.joc.9b02826","article-title":"Origins of Chemoselectivity in the Ni-Catalyzed Biaryl and Pd-Catalyzed Acyl Suzuki\u2013Miyaura Cross-Coupling of N-Acetyl-Amides","volume":"85","author":"Li","year":"2020","journal-title":"J. Org. Chem."},{"key":"2026102111012685000_cit57","doi-asserted-by":"publisher","first-page":"34575","DOI":"10.1021\/jacs.5c09306","article-title":"Unraveling the Dichotomy Exerted by Boron Reagents in Site-Selective Functionalization of C(sp2)\u2013and C(sp3)\u2013OMe Bonds","volume":"147","author":"Chen","year":"2025","journal-title":"J. Am. Chem. Soc."},{"key":"2026102111012685000_cit58","doi-asserted-by":"publisher","first-page":"8936","DOI":"10.1021\/jacs.5c21886","article-title":"Mechanistically Guided Functionalization of \u03b1,\u03b1-Disubstituted Alkenyl Amides Enabled by a Conformationally Flexible Directing Auxiliary","volume":"148","author":"Lisboa","year":"2026","journal-title":"J. Am. Chem. Soc."},{"key":"2026102111012685000_cit59","doi-asserted-by":"publisher","first-page":"9608","DOI":"10.1021\/jacs.5c20533","article-title":"Mechanistic Insights into Photoredox\/Nickel Dual-Catalyzed Difunctionalization of Alkynes: Revealing Roles of Noninnocent P-Ligand and Origins of Selectivities","volume":"148","author":"Xu","year":"2026","journal-title":"J. Am. Chem. Soc."},{"key":"2026102111012685000_cit60","doi-asserted-by":"publisher","first-page":"875","DOI":"10.1039\/tf9353100875","article-title":"Some Applications of the Transition State Method to the Calculation of Reaction Velocities, Especially in Solution","volume":"31","author":"Evans","year":"1935","journal-title":"Trans. Faraday Soc."}],"container-title":["The Journal of Organic Chemistry"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/acs.joc.6c01402","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/joceah\/article-pdf\/doi\/10.1021\/acs.joc.6c01402\/68930262\/jo-2026-01402p.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/joceah\/article-pdf\/doi\/10.1021\/acs.joc.6c01402\/68930262\/jo-2026-01402p.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,10,21]],"date-time":"2026-10-21T15:10:22Z","timestamp":1792595422000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/joceah\/article\/doi\/10.1021\/acs.joc.6c01402\/5455369\/Mechanism-and-Origin-of-Regio-and"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,10,21]]},"references-count":60,"URL":"https:\/\/doi.org\/10.1021\/acs.joc.6c01402","relation":{},"ISSN":["0022-3263","1520-6904"],"issn-type":[{"value":"0022-3263","type":"print"},{"value":"1520-6904","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,10,21]]}}}