Preparation of Potassium Acyltrifluoroborates (KATs) from Carboxylic Acids by Copper‐Catalyzed Borylation of Mixed Anhydrides**

Tung, Pinku; Schuhmacher, Anne; Schilling, Philipp E.; Bode, Jeffrey W.; Mankad, Neal P.

doi:10.1002/ange.202114513

Preparation of Potassium Acyltrifluoroborates (KATs) from Carboxylic Acids by Copper‐Catalyzed Borylation of Mixed Anhydrides**

Journal Article · Thu Dec 30 00:00:00 EST 2021 · Angewandte Chemie

DOI:https://doi.org/10.1002/ange.202114513· OSTI ID:1837845

Tung, Pinku ^[1]; Schuhmacher, Anne ^[2]; Schilling, Philipp E. ^[2]; Bode, Jeffrey W. ^[2]; ^[1]

Department of Chemistry University of Illinois at Chicago 845 W. Taylor St. Chicago Il 60607 USA
Laboratory of Organic Chemistry ETH Zurich Vladimir-Prelog-Weg 3 8093 Zurich Switzerland

Abstract

We report the preparation of potassium acyltrifluoroborates (KATs) from widely available carboxylic acids. Mixed anhydrides of carboxylic acids were prepared using isobutyl chloroformate and transformed to the corresponding KATs using a commercial copper catalyst, B ₂ (pin) ₂ , and aqueous KHF ₂ . This method allows for the facile preparation of aliphatic, aromatic, and amino acid‐derived KATs and is compatible with a variety of functional groups including alkenes, esters, halides, nitriles, and protected amines.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0021055

OSTI ID:: 1837845

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 7 Vol. 134; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (44)

Amide-Forming Ligation of Acyltrifluoroborates and Hydroxylamines in Water Dumas, Aaron M.; Molander, Gary A.; Bode, Jeffrey W. Angewandte Chemie, Vol. 124, Issue 23 https://doi.org/10.1002/ange.201201077	journal	April 2012
Oxidative Geminal Functionalization of Organoboron Compounds He, Zhi; Trinchera, Piera; Adachi, Shinya Angewandte Chemie, Vol. 124, Issue 44 https://doi.org/10.1002/ange.201206501	journal	October 2012
A Reagent for the One-Step Preparation of Potassium Acyltrifluoroborates (KATs) from Aryl- and Heteroarylhalides Erős, Gábor; Kushida, Yo; Bode, Jeffrey W. Angewandte Chemie, Vol. 126, Issue 29 https://doi.org/10.1002/ange.201403931	journal	May 2014
Catalytic Borylation using an Air‐Stable Zinc Boryl Reagent: Systematic Access to Elusive Acylboranes Campos, Jesús; Aldridge, Simon Angewandte Chemie, Vol. 127, Issue 47 https://doi.org/10.1002/ange.201507627	journal	September 2015
Direct Access to MIDA Acylboronates through Mild Oxidation of MIDA Vinylboronates Lepage, Mathieu L.; Lai, Samson; Peressin, Nicolas Angewandte Chemie, Vol. 129, Issue 48 https://doi.org/10.1002/ange.201707125	journal	October 2017
Synthesis of Acylborons by Ozonolysis of Alkenylboronates: Preparation of an Enantioenriched Amino Acid Acylboronate Taguchi, Jumpei; Ikeda, Toshiki; Takahashi, Rina Angewandte Chemie, Vol. 129, Issue 44 https://doi.org/10.1002/ange.201707933	journal	September 2017
Concise Synthesis of Potassium Acyltrifluoroborates from Aldehydes through Copper(I)‐Catalyzed Borylation/Oxidation Taguchi, Jumpei; Takeuchi, Takumi; Takahashi, Rina Angewandte Chemie, Vol. 131, Issue 22 https://doi.org/10.1002/ange.201901748	journal	March 2019
Katalytische Synthese von Kaliumacyltrifluoroboraten mithilfe chemoselektiver Kreuzkupplung eines bifunktionalen Reagenzes Wu, Dino; Fohn, Nicole A.; Bode, Jeffrey W. Angewandte Chemie, Vol. 131, Issue 32 https://doi.org/10.1002/ange.201904576	journal	July 2019
Diversity‐Oriented Synthesis of α‐Functionalized Acylborons and Borylated Heteroarenes by Nucleophilic Ring Opening of α‐Chloroepoxyboronates Tan, Dong‐Hang; Cai, Yuan‐Hong; Zeng, Yao‐Fu Angewandte Chemie, Vol. 131, Issue 39 https://doi.org/10.1002/ange.201907349	journal	July 2019
Synthesis of Polymers Containing Potassium Acyltrifluoroborates (KATs) and Post‐polymerization Ligation and Conjugation Schauenburg, Dominik; Divandari, Mohammad; Neumann, Kevin Angewandte Chemie, Vol. 132, Issue 34 https://doi.org/10.1002/ange.202006273	journal	July 2020
One‐Step Synthesis of Acylboron Compounds via Copper‐Catalyzed Carbonylative Borylation of Alkyl Halides** Cheng, Li‐Jie; Zhao, Siling; Mankad, Neal P. Angewandte Chemie, Vol. 133, Issue 4 https://doi.org/10.1002/ange.202012373	journal	November 2020
Katalytische Synthese von Kaliumacyltrifluoroboraten (KATs) aus Boronsäuren und dem Thioimidat‐KAT‐Transferreagenz Schuhmacher, Anne; Ryan, Sarah J.; Bode, Jeffrey W. Angewandte Chemie, Vol. 133, Issue 8 https://doi.org/10.1002/ange.202014581	journal	December 2020
Amide-Forming Ligation of Acyltrifluoroborates and Hydroxylamines in Water Dumas, Aaron M.; Molander, Gary A.; Bode, Jeffrey W. Angewandte Chemie International Edition, Vol. 51, Issue 23 https://doi.org/10.1002/anie.201201077	journal	April 2012
Oxidative Geminal Functionalization of Organoboron Compounds He, Zhi; Trinchera, Piera; Adachi, Shinya Angewandte Chemie International Edition, Vol. 51, Issue 44 https://doi.org/10.1002/anie.201206501	journal	October 2012
A Reagent for the One-Step Preparation of Potassium Acyltrifluoroborates (KATs) from Aryl- and Heteroarylhalides Erős, Gábor; Kushida, Yo; Bode, Jeffrey W. Angewandte Chemie International Edition, Vol. 53, Issue 29 https://doi.org/10.1002/anie.201403931	journal	May 2014
Catalytic Borylation using an Air-Stable Zinc Boryl Reagent: Systematic Access to Elusive Acylboranes Campos, Jesús; Aldridge, Simon Angewandte Chemie International Edition, Vol. 54, Issue 47 https://doi.org/10.1002/anie.201507627	journal	September 2015
Direct Access to MIDA Acylboronates through Mild Oxidation of MIDA Vinylboronates Lepage, Mathieu L.; Lai, Samson; Peressin, Nicolas Angewandte Chemie International Edition, Vol. 56, Issue 48 https://doi.org/10.1002/anie.201707125	journal	October 2017
Synthesis of Acylborons by Ozonolysis of Alkenylboronates: Preparation of an Enantioenriched Amino Acid Acylboronate Taguchi, Jumpei; Ikeda, Toshiki; Takahashi, Rina Angewandte Chemie International Edition, Vol. 56, Issue 44 https://doi.org/10.1002/anie.201707933	journal	September 2017
Concise Synthesis of Potassium Acyltrifluoroborates from Aldehydes through Copper(I)‐Catalyzed Borylation/Oxidation Taguchi, Jumpei; Takeuchi, Takumi; Takahashi, Rina Angewandte Chemie International Edition, Vol. 58, Issue 22 https://doi.org/10.1002/anie.201901748	journal	May 2019
Catalytic Synthesis of Potassium Acyltrifluoroborates (KATs) through Chemoselective Cross‐Coupling with a Bifunctional Reagent Wu, Dino; Fohn, Nicole A.; Bode, Jeffrey W. Angewandte Chemie International Edition, Vol. 58, Issue 32 https://doi.org/10.1002/anie.201904576	journal	August 2019
Diversity‐Oriented Synthesis of α‐Functionalized Acylborons and Borylated Heteroarenes by Nucleophilic Ring Opening of α‐Chloroepoxyboronates Tan, Dong‐Hang; Cai, Yuan‐Hong; Zeng, Yao‐Fu Angewandte Chemie International Edition, Vol. 58, Issue 39 https://doi.org/10.1002/anie.201907349	journal	September 2019
Synthesis of Polymers Containing Potassium Acyltrifluoroborates (KATs) and Post‐polymerization Ligation and Conjugation Schauenburg, Dominik; Divandari, Mohammad; Neumann, Kevin Angewandte Chemie International Edition, Vol. 59, Issue 34 https://doi.org/10.1002/anie.202006273	journal	July 2020
One‐Step Synthesis of Acylboron Compounds via Copper‐Catalyzed Carbonylative Borylation of Alkyl Halides** Cheng, Li‐Jie; Zhao, Siling; Mankad, Neal P. Angewandte Chemie International Edition, Vol. 60, Issue 4 https://doi.org/10.1002/anie.202012373	journal	November 2020
Catalytic Synthesis of Potassium Acyltrifluoroborates (KATs) from Boronic Acids and the Thioimidate KAT Transfer Reagent Schuhmacher, Anne; Ryan, Sarah J.; Bode, Jeffrey W. Angewandte Chemie International Edition, Vol. 60, Issue 8 https://doi.org/10.1002/anie.202014581	journal	December 2020
Potassium Acyltrifluoroborate (KAT) Ligations are Orthogonal to Thiol- Michael and SPAAC Reactions: Covalent Dual Immobilization of Proteins onto Synthetic PEG Hydrogels Mazunin, Dmitry; Bode, Jeffrey W. Helvetica Chimica Acta, Vol. 100, Issue 2 https://doi.org/10.1002/hlca.201600311	journal	February 2017
Chemoselective derivitization of folded synthetic insulin variants with potassium acyltrifluoroborates (KATs) Boross, Gabor N.; Schauenburg, Dominik; Bode, Jeffrey W. Helvetica Chimica Acta https://doi.org/10.1002/hlca.201800214	journal	December 2018
Copper-Catalyzed Carbonylative Coupling of Alkyl Halides Cheng, Li-Jie; Mankad, Neal P. Accounts of Chemical Research, Vol. 54, Issue 9 https://doi.org/10.1021/acs.accounts.1c00115	journal	April 2021
Methodologies and Strategies for Selective Borylation of C–Het and C–C Bonds Wang, Minyan; Shi, Zhuangzhi Chemical Reviews, Vol. 120, Issue 15 https://doi.org/10.1021/acs.chemrev.9b00384	journal	June 2020
Condensation-Driven Assembly of Boron-Containing Bis(Heteroaryl) Motifs Using a Linchpin Approach Adachi, Shinya; Liew, Sean K.; Lee, C. Frank Organic Letters, Vol. 17, Issue 22 https://doi.org/10.1021/acs.orglett.5b02741	journal	November 2015
One-Step Synthesis of Aliphatic Potassium Acyltrifluoroborates (KATs) from Organocuprates Liu, Sizhou M.; Wu, Dino; Bode, Jeffrey W. Organic Letters, Vol. 20, Issue 8 https://doi.org/10.1021/acs.orglett.8b00720	journal	April 2018
Synthesis of Biocompatible PEG Hydrogels by pH-Sensitive Potassium Acyltrifluoroborate (KAT) Amide Ligations Mazunin, Dmitry; Broguiere, Nicolas; Zenobi-Wong, Marcy ACS Biomaterials Science & Engineering, Vol. 1, Issue 6 https://doi.org/10.1021/acsbiomaterials.5b00145	journal	May 2015
PEGylation and Dimerization of Expressed Proteins under Near Equimolar Conditions with Potassium 2-Pyridyl Acyltrifluoroborates White, Christopher J.; Bode, Jeffrey W. ACS Central Science, Vol. 4, Issue 2 https://doi.org/10.1021/acscentsci.7b00432	journal	January 2018
Reinvestigation of the mixed carbonic anhydride method of peptide synthesis Anderson, George Washington.; Zimmerman, Joan E.; Callahan, Francis M. Journal of the American Chemical Society, Vol. 89, Issue 19 https://doi.org/10.1021/ja00995a032	journal	September 1967
Rapid Ligations with Equimolar Reactants in Water with the Potassium Acyltrifluoroborate (KAT) Amide Formation Noda, Hidetoshi; Erős, Gábor; Bode, Jeffrey W. Journal of the American Chemical Society, Vol. 136, Issue 15 https://doi.org/10.1021/ja5018442	journal	April 2014
Chemoselective Acylation of Primary Amines and Amides with Potassium Acyltrifluoroborates under Acidic Conditions Gálvez, Alberto Osuna; Schaack, Cédric P.; Noda, Hidetoshi Journal of the American Chemical Society, Vol. 139, Issue 5 https://doi.org/10.1021/jacs.7b00059	journal	January 2017
Leaving Groups as Traceless Topological Modifiers for the Synthesis of Topologically Isomeric Polymer Networks Gu, Yuwei; Schauenburg, Dominik; Bode, Jeffrey W. Journal of the American Chemical Society, Vol. 140, Issue 43 https://doi.org/10.1021/jacs.8b07967	journal	October 2018
Synthesis of Acyltrifluoroborates Dumas, Aaron M.; Bode, Jeffrey W. Organic Letters, Vol. 14, Issue 8 https://doi.org/10.1021/ol300668m	journal	April 2012
CO ₂ Offgas as a Mechanistic Probe and Scale-up Tool in N-Acylations Using Mixed Anhydrides from Amino Acids and Isobutyl Chloroformate Chaudhary, Apurva; Girgis, Michael J.; Prashad, Mahavir Organic Process Research & Development, Vol. 7, Issue 6 https://doi.org/10.1021/op034085a	journal	October 2003
Synthesis and reactivities of monofluoro acylboronates in chemoselective amide bond forming ligation with hydroxylamines Noda, Hidetoshi; Bode, Jeffrey W. Organic & Biomolecular Chemistry, Vol. 14, Issue 1 https://doi.org/10.1039/C5OB02118A	journal	January 2016
Facile synthesis of α-aminoboronic acids from amines and potassium acyltrifluoroborates (KATs) via trifluoroborate-iminiums (TIMs) Shiro, Tomoya; Schuhmacher, Anne; Jackl, Moritz K. Chemical Science, Vol. 9, Issue 23 https://doi.org/10.1039/C8SC01486H	journal	January 2018
Covalently functionalized amide cross-linked hydrogels from primary amines and polyethylene glycol acyltrifluoroborates (PEG-KATs) Schauenburg, Dominik; Osuna Gálvez, Alberto; Bode, Jeffrey W. Journal of Materials Chemistry B, Vol. 6, Issue 29 https://doi.org/10.1039/C8TB01028E	journal	January 2018
Chemoselective ¹⁸ F-incorporation into pyridyl acyltrifluoroborates for rapid radiolabelling of peptides and proteins at room temperature Chiotellis, Aristeidis; Ahmed, Hazem; Betzel, Thomas Chemical Communications, Vol. 56, Issue 5 https://doi.org/10.1039/C9CC08645E	journal	January 2020
A modular and concise approach to MIDA acylboronates via chemoselective oxidation of unsymmetrical geminal diborylalkanes: unlocking access to a novel class of acylborons Lin, Shengjia; Wang, Lucia; Aminoleslami, Negin Chemical Science, Vol. 10, Issue 17 https://doi.org/10.1039/C9SC00378A	journal	January 2019
Boryllithium: Isolation, Characterization, and Reactivity as a Boryl Anion Segawa, Y.; Yamashita, M.; Nozaki, K. Science, Vol. 314, Issue 5796 https://doi.org/10.1126/science.1131914	journal	October 2006

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