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Aldrichimica Acta VOLUME 51, NO. 1 | 2018 ALDRICHIMICA ACTA The Spectacular Resurgence of Electrochemical Redox Reactions in Organic Synthesis Carbon–Carbon π Bonds as Conjunctive Reagents in Cross-Coupling The life science business of Merck KGaA, Darmstadt, Germany operates as MilliporeSigma in the U.S. and Canada. MakInG sTrIDes In Genome EDITInG: THe DIGITaL, CHemIcaL, anD BIoLogIcaL Dear Fellow Researchers: You may not know that MilliporeSigma can make DNA from scratch, using 100% synthetic chemical methods—no living cells and no fermentation necessary. Our DNA synthesis facilities in The Woodlands (Texas) and Haverhill (U.K.) receive thousands of DNA orders daily from scientists all over the world. A small piece of DNA, one hundred bases long, gives scientists 4100 possibilities using only the fundamental letters of our genetic code (A,C,G,T). Included within these options is the opportunity for a researcher to open a common text editor on his or her PC and design a 100-base piece of DNA. This piece of DNA could help study diseases ranging from sickle cell anemia and blindness to cystic fibrosis by using CRISPR. To get started, scientists cut this 100-base DNA text from the text editor and paste it into MilliporeSigma’s online ordering system. The corresponding DNA piece that likely has never existed before is then delivered to them in 24–48 hours. Once received, this piece of DNA is mixed with CRISPR and living cells, and, with a “blast” of electricity, these synthetic chemical pieces activate the cell to edit the genome. Learn more about our CRISPR gene editing portfolio at SigmaAldrich.com/CRISPR Sincerely yours, Udit Batra, Ph.D. CEO, MilliporeSigma The life science business of Merck KGaA, Darmstadt, Germany operates as MilliporeSigma in the U.S. and Canada. Copyright © 2018 Merck KGaA, Darmstadt, Germany and/or its Affiliates. All Rights Reserved. ALDRICHIMICA ACTA VOL. 51, NO. 1 • 2018 “PLEASE BOTHER US.” Dear Fellow Chemists, Professor Timothy Newhouse of the Department of Chemistry at Yale University kindly suggested that we offer N-cyclohexyl-2,6-bis(1- Merck KGaA, Darmstadt, Germany methylethyl)benzenamine (CyanH, 809527), a hindered monodentate Frankfurter Strasse 250 aniline derivative and a stable precursor of the novel, recyclable reagent 64293 Darmstadt, Germany lithium N-cyclohexylanilide (LiCyan). LiCyan is used in situ to effect the Phone +49 6151 72 0 palladium-catalyzed, direct α,β-dehydrogenation of amides in good-to-high yields. This practical method has a wide substrate scope and tolerates OH and NH functional groups, eliminating the To Place Orders / Customer Service need for additional reaction steps to protect and deprotect them. Contact your local office or visit Chen, Y.; Turlik, A.; Newhouse, T. R. J. Am. Chem. Soc. 2016, 138, 1166. SigmaAldrich.com/order Technical Service i-Pr i-Pr Contact your local office or visit N H SigmaAldrich.com/techinfo 809527 General Correspondence Editor: Sharbil J. Firsan, Ph.D. InChI Key: YDWZEQMCJKBGTO-UHFFFAOYSA-N [email protected] 809527 N-Cyclohexyl-2,6-bis(1-methylethyl)benzenamine (CyanH) 1 g Subscriptions We welcome your product ideas. Do you need a product that is not featured on our website? Request your FREE subscription to the Ask us! For more than 60 years, your research needs and suggestions have shaped our product Aldrichimica Acta at SigmaAldrich.com/acta offering. Email your suggestion to [email protected]. Udit Batra, Ph.D. CEO, MilliporeSigma TABLE OF CONTENTS The Spectacular Resurgence of Electrochemical Redox Reactions in Organic Synthesis. 3 Pierre-Georges Echeverria,* Dominique Delbrayelle, Aurélien Letort, Fiona Nomertin, Marc Perez, and Laurent Petit, Minakem Recherche (France) Carbon–Carbon π Bonds as Conjunctive Reagents in Cross-Coupling . 21 Joseph Derosa, Van T. Tran, Vincent A. van der Puyl, and Keary M. Engle,* The Scripps Research Institute (La Jolla) ABOUT OUR COVER Ginevra de' Benci (oil on panel, 38.1 × 37 cm, ca. 1474/1478) is one of Leonardo da Vinci’s (1452–1519) earliest works. Raised in an affluent family, he received a conventional education and apprenticed for several years as a painter and sculptor The entire Aldrichimica Acta archive is available with Andrea del Verrocchio in Florence. Blessed with an at SigmaAldrich.com/acta extraordinary intellect and love of learning, Leonardo also immersed himself throughout his life in the study of Aldrichimica Acta (ISSN 0002-5100) is a what we call today anatomy, engineering, architecture, publication of Merck KGaA, Darmstadt, and mechanics, and left a legacy of important works in Germany. various fields of knowledge. As an artist, he worked for various wealthy, aristocratic, and royal patrons in Florence, Copyright © 2018 Merck KGaA, Darmstadt, Milan, Rome, and France. While da Vinci created only a Germany and/or its affiliates. All Rights small number of paintings, his compositions have strongly Reserved. MilliporeSigma, the vibrant M influenced later generations of artists, and a number of Detail from Ginevra de' Benci. Photo courtesy National Gallery of Art, Washington, DC. and Sigma-Aldrich are trademarks of Merck his paintings are now considered masterpieces of all time. KGaA, Darmstadt, Germany or its affiliates. Ginevra de' Benci is the obverse* side of a two-sided panel that was commissioned, as All other trademarks are the property of their customary, on the occasion of the subject’s engagement or marriage. This portrait of the beautiful, respective owners. Detailed information on but solemn and detached, 16-year-old is so flawlessly executed and lifelike that one is forgiven trademarks is available via publicly accessible for believing one is in the presence of Ginevra herself. Leonardo’s strong interest in, and keen resources. Purchaser must determine the sense of observation of, the natural world as well as his break with tradition by placing Ginevra in suitability of the products for their particular a three-quarter pose in an outdoor, “natural”, setting is an early indication of how his realistic and use. Additional terms and conditions may expressive scenes would influence and change fine art in the Renaissance. apply. Please see product information on the Purchased for the National Gallery of Art, Washington, DC, through the Ailsa Mellon Bruce Fund. Sigma-Aldrich website at SigmaAldrich.com and/or on the reverse side of the invoice or * So, what is on the reverse side of the Ginevra de' Benci panel? To find out, visit packing slip. SigmaAldrich.com/acta511 Navigate toward Metabolomic Discovery Explore our portfolio: • Comprehensive metabolomic resources, reagents and kits • Large collection of amino acid metabolites and carbohydrate metabolites • Enzymatic-based kits for the quantitation of nutrients and metabolites SigmaAldrich.com/metabolomics The life science business of Merck KGaA, Darmstadt, Germany operates as MilliporeSigma in the U.S. and Canada. © 2018 Merck KGaA, Darmstadt, Germany and/or its affiliates. All Rights Reserved. MilliporeSigma, Sigma-Aldrich, and the vibrant M are trademarks of Merck KGaA, Darmstadt, Germany or its affiliates. All other trademarks are the property of their respective owners. Detailed information on trademarks is available via publicly accessible resources. Aldrichimica ACTA 3 VOL. 51, NO. 1 • 2018 The Spectacular Resurgence of Electrochemical Redox Reactions in Organic Synthesis Dr. P.-G. Echeverria Dr. A. Letort Dr. M. Perez Mr. D. Delbrayelle Ms. F. Nomertin Dr. L. Petit Pierre-Georges Echeverria,* Dominique Delbrayelle, Aurélien Letort, Fiona Nomertin, Marc Perez, and Laurent Petit Dedicated to the Minakem Recherche memory of Prof. 145 Chemin des Lilas Dr. István E. Markó 59310 Beuvry la Forêt, France Email: [email protected] Keywords. organic electrosynthesis; radicals; anodic oxidation; 3.2.3. C–O Bond cathodic reduction; paired electrosynthesis. 3.2.4. C–S Bond 3.2.5. C–Cl Bond Abstract. Electrochemistry has had a profound impact on green 3.3. N–Y Bond Formation chemistry and in applications such as energy conversion and 3.3.1. N–N Bond storage, electroplating, water treatment, and environmental 3.3.2. N–S Bond monitoring, and it has also been embraced by various 3.4. Shono Oxidation industries. It is therefore quite surprising that electrochemistry 3.5. Miscellaneous Reactions has seldom been used by synthetic organic chemists. This could 3.5.1. [3 + 2] Annulation be partly attributed to the misconception that the electron as a 3.5.2. Fluorination reagent cannot be tamed easily. In recent years, the application 3.5.3. Other Reactions of electrochemistry to the synthesis of fine chemicals has 4. Cathodic Reduction had a resurgence, and many elegant solutions based on 4.1. C–Y Bond Formation electrochemistry have been devised to address synthetic 4.1.1. C–C Bond challenges with easy-to-use experimental setups. 4.1.2. C–B Bond 4.1.3. C–O Bond Outline 4.2. Markó-Lam Reduction 1. Introduction 4.3. Dehalogenation 2. Basic Principles 4.4. Cyclopropane Synthesis 2.1. The Electrochemical Cell and Cathode and Anode 4.5. Electrogenerated Bases Reactions 4.5.1. β-Lactam Synthesis 2.2. Mediators and Electroauxiliaries 4.5.2. C–N Bond Formation 3. Anodic Oxidation 4.5.3. C–C Bond Formation 3.1. Alcohol Oxidation 5. Paired Electrosynthesis 3.2. C–Y Bond Formation 6. Conclusion and Outlook 3.2.1. C–C Bond 7. Acknowledgment 3.2.2. C–N Bond 8. References The Spectacular Resurgence of Electrochemical Redox Reactions in Organic Synthesis 4 Pierre-Georges Echeverria,* Dominique Delbrayelle, Aurélien Letort, Fiona Nomertin, Marc Perez, and Laurent Petit 1. Introduction in this way, notably because the oxidation or reduction Chemistry is all about electrons. This general statement, potential required is too high in absolute value, giving rise to though simple, is nonetheless true. In organic chemistry, many side reactions or electrode passivation, or is even beyond the transformations are redox reactions, involving electrons being accessible range due to degradative electrolysis of the solvent or added to, or removed from, the molecule of interest.
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