@article{lalloo_brigham_sanford_2023, title={Correction to “Mechanism-Driven Development of Group 10 Metal-Catalyzed Decarbonylative Coupling Reactions”}, url={https://doi.org/10.1021/acs.accounts.3c00277}, DOI={10.1021/acs.accounts.3c00277}, abstractNote={ADVERTISEMENT RETURN TO ISSUEPREVAddition/CorrectionNEXTORIGINAL ARTICLEThis notice is a correctionCorrection to “Mechanism-Driven Development of Group 10 Metal-Catalyzed Decarbonylative Coupling Reactions”Naish LallooNaish LallooMore by Naish Lalloohttps://orcid.org/0000-0001-9926-0387, Conor E. BrighamConor E. BrighamMore by Conor E. Brigham, and Melanie S. SanfordMelanie S. SanfordMore by Melanie S. Sanfordhttps://orcid.org/0000-0001-9342-9436Cite this: Acc. Chem. Res. 2023, 56, 12, 1683Publication Date (Web):May 25, 2023Publication History Received11 May 2023Published online25 May 2023Published inissue 20 June 2023https://doi.org/10.1021/acs.accounts.3c00277Copyright © 2023 American Chemical SocietyRIGHTS & PERMISSIONSArticle Views633Altmetric-Citations-LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (728 KB) Get e-Alertsclose Get e-Alerts}, journal={Accounts of Chemical Research}, author={Lalloo, Naish and Brigham, Conor E. and Sanford, Melanie S.}, year={2023}, month={Jun} }
 @article{bunnell_lalloo_brigham_sanford_2023, title={Palladium-Catalyzed Decarbonylative Coupling of (Hetero)Aryl Boronate Esters with Difluorobenzyl Glutarimides}, url={https://doi.org/10.1021/acs.orglett.3c03071}, DOI={10.1021/acs.orglett.3c03071}, abstractNote={This report describes the Pd-catalyzed decarbonylative coupling of difluorobenzyl glutarimides with (hetero)aryl boronate esters to yield difluorobenzyl-substituted (hetero)arene products. The use of PAd2Bu as the phosphine ligand in combination with neopentylboronate ester nucleophiles proved critical for the selective formation of the decarbonylative coupling product versus analogous difluorobenzyl ketone. This transformation is effective for electronically diverse (hetero)aryl boronate esters and substituted difluorobenzyl glutarimides.}, journal={Organic Letters}, author={Bunnell, Alexander and Lalloo, Naish and Brigham, Conor and Sanford, Melanie S.}, year={2023}, month={Oct} }
 @article{lalloo_brigham_sanford_2022, title={Mechanism-Driven Development of Group 10 Metal-Catalyzed Decarbonylative Coupling Reactions}, url={https://doi.org/10.1021/acs.accounts.2c00496}, DOI={10.1021/acs.accounts.2c00496}, abstractNote={ConspectusTransition-metal-catalyzed cross-coupling reactions are widely used in both academia and industry for the construction of carbon-carbon and carbon-heteroatom bonds. The vast majority of cross-coupling reactions utilize aryl (pseudo)halides as the electrophilic coupling partner. Carboxylic acid derivatives (RC(O)X) represent a complementary class of electrophiles that can engage in decarbonylative couplings to produce analogous products. This decarbonylative approach offers the advantage that RC(O)X are abundant and inexpensive. In addition, decarbonylative coupling enables both intramolecular (between R and X of the carboxylic acid derivative) as well as intermolecular bond-forming reactions (in which an exogeneous nucleophile is coupled with the R group derived from RC(O)X). In these intermolecular reactions, the X-substituent on the carboxylic acid can be tuned to facilitate both oxidative addition and transmetalation, thus eliminating the need for an exogeneous base. This Account details our group's development of a diverse variety of base-free decarbonylative coupling reactions catalyzed by group 10 metals. Furthermore, it highlights how catalyst design can be guided by stoichiometric organometallic studies of these systems.Our early studies focused on intramolecular decarbonylative couplings that transform RC(O)X to the corresponding R-X with extrusion of CO. We first identified Pd and Ni monodentate phosphine catalysts that convert aryl thioesters (ArC(O)SR) to the corresponding thioethers (ArSR). We next expanded this reactivity to fluoroalkyl thioesters, using readily available fluoroalkyl carboxylic acids as the fluoroalkyl (RF) source. A Ni-phosphinoferrocene catalyst proved optimal, and the large bite angle bidentate ligand was necessary to promote the challenging RF-S bond-forming reductive elimination step.We next pursued intramolecular decarbonylative couplings of aroyl halides. Palladium-based catalysts bearing dialkylbiaryl ligands (e.g., BrettPhos) were identified as optimal for converting aroyl chlorides (ArC(O)Cl) to aryl chlorides (ArCl). These ligands were selected based on their ability to facilitate the key C-Cl bond-forming reductive elimination step of the catalytic cycle. In contrast, all attempts to convert aroyl fluorides [ArC(O)F)] to aryl fluorides (ArF) were unsuccessful with either Pd- or Ni-based catalysts. Organometallic studies of the Ni-system show that C(O)-F oxidative addition and CO deinsertion proceed smoothly, but the resulting nickel(II) aryl fluoride intermediate fails to undergo C-F bond-forming reductive elimination.In contrast to its inertness to reductive elimination, this nickel(II) aryl fluoride proved highly reactive toward transmetalation. The fluoride ligand serves as an internal base, such that no additional base is required. We leveraged this "transmetalation active" intermediate to achieve base-free Ni-catalyzed intermolecular decarbonylative coupling reactions between aroyl fluorides and boron reagents to access both biaryl and aryl-boronate ester products. By tuning the electrophile, transmetalating reagent, and catalyst, this same approach also proved applicable to base-free intermolecular decarbonylative fluoroalkylation (between difluoromethylacetyl fluoride and arylboronate esters) and aryl amination (between phenol esters and silyl amines).Moving forward, a key goal is to identify catalyst systems that enable more challenging bond constructions via this manifold. In addition, CO inhibition remains a major issue leading to the requirement for high temperatures and high catalyst loadings. Identifying catalysts that are resistant to CO binding and/or approaches to remove CO under mild conditions will be critical for making these reactions more practical and scalable.}, journal={Accounts of Chemical Research}, author={Lalloo, Naish and Brigham, Conor E. and Sanford, Melanie S.}, year={2022}, month={Dec} }
 @article{lalloo_malapit_taimoory_brigham_sanford_2021, title={Decarbonylative Fluoroalkylation at Palladium(II): From Fundamental Organometallic Studies to Catalysis}, volume={10}, url={https://doi.org/10.1021/jacs.1c08551}, DOI={10.1021/jacs.1c08551}, abstractNote={This Article describes the development of a decarbonylative Pd-catalyzed aryl-fluoroalkyl bond-forming reaction that couples fluoroalkylcarboxylic acid-derived electrophiles [RFC(O)X] with aryl organometallics (Ar-M'). This reaction was optimized by interrogating the individual steps of the catalytic cycle (oxidative addition, carbonyl de-insertion, transmetalation, and reductive elimination) to identify a compatible pair of coupling partners and an appropriate Pd catalyst. These stoichiometric organometallic studies revealed several critical elements for reaction design. First, uncatalyzed background reactions between RFC(O)X and Ar-M' can be avoided by using M' = boronate ester. Second, carbonyl de-insertion and Ar-RF reductive elimination are the two slowest steps of the catalytic cycle when RF = CF3. Both steps are dramatically accelerated upon changing to RF = CHF2. Computational studies reveal that a favorable F2C-H---X interaction contributes to accelerating carbonyl de-insertion in this system. Finally, transmetalation is slow with X = difluoroacetate but fast with X = F. Ultimately, these studies enabled the development of an (SPhos)Pd-catalyzed decarbonylative difluoromethylation of aryl neopentylglycol boronate esters with difluoroacetyl fluoride.}, journal={Journal of the American Chemical Society}, publisher={American Chemical Society (ACS)}, author={Lalloo, Naish and Malapit, Christian A. and Taimoory, S. Maryamdokht and Brigham, Conor E. and Sanford, Melanie S.}, year={2021}, month={Nov} }
 @inproceedings{lalloo_2021, title={Development of Pd-catalyzed Decarbonylative Difluoromethylation of Arenes}, booktitle={ACS National Spring Meeting}, author={Lalloo, N.}, year={2021}, month={Apr} }
 @inproceedings{lalloo_2020, title={Development of Pd-catalyzed Decarbonylative Difluoromethylation of Arenes}, booktitle={Isabella & Jerome Karle Symposium}, author={Lalloo, N.}, year={2020}, month={Aug} }
 @article{brigham_malapit_lalloo_sanford_2020, title={Nickel-Catalyzed Decarbonylative Synthesis of Fluoroalkyl Thioethers}, volume={10}, ISSN={2155-5435 2155-5435}, url={http://dx.doi.org/10.1021/acscatal.0c02950}, DOI={10.1021/acscatal.0c02950}, abstractNote={This report describes the development of a nickel-catalyzed decarbonylative reaction for the synthesis of fluoroalkyl thioethers (RFSR) from the corresponding thioesters. Readily available, inexpensive, and stable fluoroalkyl carboxylic acids (RFCO2H) serve as the fluoroalkyl (RF) source in this transformation. Stoichiometric organometallic studies reveal that RF–S bond-forming reductive elimination is a challenging step in the catalytic cycle. This led to the identification of diphenylphosphinoferrocene as the optimal ligand for this transformation. Ultimately, this method was applied to the construction of diverse fluoroalkyl thioethers (RFSR), with R = both aryl and alkyl.}, number={15}, journal={ACS Catalysis}, publisher={American Chemical Society (ACS)}, author={Brigham, Conor E. and Malapit, Christian A. and Lalloo, Naish and Sanford, Melanie S.}, year={2020}, month={Jul}, pages={8315–8320} }
 @inproceedings{lalloo_2019, title={Advances in Aqueous Platinum(II)-Catalyzed C(sp3)–H Oxidation Reactions}, booktitle={257th ACS National Meeting and Expo}, author={Lalloo, N.}, year={2019}, month={Apr} }