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Palladium-Catalyzed Molybdenum Hexacarbonyl-Mediated Gas-Free Carbonylative Reactions

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Palladium-Catalyzed Molybdenum Hexacarbonyl-Mediated Gas-Free Carbonylative Reactions SYNLETT0936-52141437-2096 © Georg Thieme Verlag Stuttgart · New York 2019, 30, 141–155 account 141 en Syn lett L. Åkerbladh et al. Account Palladium-Catalyzed Molybdenum Hexacarbonyl-Mediated Gas-Free Carbonylative Reactions Linda Åkerbladh Luke R. Odell* Mats Larhed* 0000-0001-6258-0635 Department of Medicinal Chemistry, Organic Pharmaceutical Chemistry, BMC, Uppsala University, Box 574, 75123 Uppsala, Sweden [email protected] [email protected] Received: 08.08.2018 plex examples of carbonylative processes and new technol- Accepted after revision: 03.09.2018 ogies such as the use of two-chamber systems for lab-scale Published online: 02.10.2018 DOI: 10.1055/s-0037-1610294; Art ID: st-2018-a0502-a synthesis and multicomponent reactions (MCRs). High- lighted methodologies were to a large extent selected from Abstract This account summarizes Pd(0)-catalyzed Mo(CO)6-mediat- the authors’ own laboratories. ed gas-free carbonylative reactions published in the period October In the late 1930s, hydroformylation with syngas (the Ro- 2011 to May 2018. Presented reactions include inter- and intramolecu- 2 lar carbonylations, carbonylative cross-couplings, and carbonylative elen reaction) and hydrocarboxylation with carbon mon- 3 multicomponent reactions using Mo(CO)6 as a solid source of CO. The oxide and water (the Reppe reaction) were discovered. presented methodologies were developed mainly for small-scale appli- However, the finding by Heck and co-workers in 1974 that cations, avoiding the problematic use of gaseous CO in a standard labo- organohalides could be carbonylatively coupled with ali- ratory. In most cases, the reported Mo(CO)6-mediated carbonylations were conducted in sealed vials or by using two-chamber solutions. phatic alcohols and amines by employing catalytic amounts 4–6 1 Introduction of Pd(0) represented a major step forward. 2 Recent Developments The use of CO as a one-carbon building block has many 2.1 New CO Sources advantages. The catalytic 1,1-insertion of the carbonyl moi- 2.2 Two-Chamber System for ex Situ CO Generation ety is highly atom-efficient and provides a valuable syn- 2.3 Multicomponent Carbonylations 3 Carbonylations with N and O Nucleophiles thetic handle for further structural elaboration of the 4 Carbonylative Cross-Coupling Reactions with Organometallics resulting carbonyl compound. Furthermore, carbonylations 5 Carbonylative Cascade Reactions are in essence three-component reactions, and by varying 6 Carbonylative Cascade, Multistep Reactions the organohalide and nucleophile component, considerable 7 Summary and Outlook product diversity can easily be achieved. Thus, Pd-catalyzed Key words carbonylation, molybdenum, multicomponent reactions, carbonylation reactions such as aminocarbonylation, This document was downloaded for personal use only. Unauthorized distribution is strictly prohibited. palladium, catalysis alkoxycarbonylations, hydroformylations, and carbonyla- tive cross-coupling reactions are now essential tools for radiochemists7,8 as well as for synthetic and medicinal 1 Introduction chemists.6,9 Despite the huge potential, the acute toxicity, flamma- There has been considerable development in the carbo- ble nature, and requirement for specialized lab equipment, nylation chemistry field since two of us authored the first such as metal reactors, in combination with the difficulty to Account on Mo(CO)6-mediated CO gas-free carbonylative detect leakages of the colorless and odorless gas have reactions.1 The use of nongaseous CO sources has achieved deterred synthetic chemists from fully applying the useful general acceptance within the synthetic organic communi- carbonylation methods despite their synthetic advantages. ty and this update covers results from more than 50 new As a result, much recent effort has been invested in devel- articles. As a consequence, this new Account, which covers oping more convenient and safer methods for handling the the literature from October 2011 to May 2018, is substan- toxic carbon monoxide gas.6,10,11,12 tially different from the first review. It contains more com- © Georg Thieme Verlag Stuttgart · New York — Synlett 2019, 30, 141–155 142 Syn lett L. Åkerbladh et al. Account 2 Recent Developments O CO O H O OC R Cl CO Cl Mo O H OH OC CO 2.1 New CO Sources O CO formateformic acid oxalyl chloride Mo(CO)6 In order to avoid handling of gaseous CO, several meth- Cl O ods employing a variety of CO precursors/sources have O CHCl3 been developed (Figure 1). One approach has been to utilize Ph + CO Si OH 2 molecules with carbonyl motifs, which by the exposure to CsOH•H2O Ph transition metals, additives, base, or heat will release CO. Examples, include alkyl- and arylformates,11,13–16 alde- COgen silacarboxylic acid hydrolysis of carbon dioxide chloroform hydes,17 formic acid,18 formamides and N-formylsaccha- rin,19–21 carbon dioxide,22,23 and metal carbonyls,24,25 such as Figure 1 Representative selection of various CO sources reported in 26,27,28 the literature the highly versatile Mo(CO)6. However, several of the mentioned CO sources require an additional transition met- al, strong base, or high temperatures to release CO gas. 2.2 Two-Chamber System for ex Situ CO Alternatively, the use of metal carbonyls will generate Generation stoichiometric amounts of another transition metal as waste. Indeed, Mo(CO)6 has been reported to possess cata- The issues with compatibility of the CO-generating re- lytic activities29,30 in addition to reducing aromatic nitro action with the CO-consuming reaction may impose severe functionalities at elevated temperatures.31 limitations on the scope of nongaseous carbonylation reac- tions. An elegant approach that circumvents these prob- lems was developed by Skrydstrup et al., in which CO was liberated ex situ following Pd-catalyzed decomposition of Biographical Sketches Linda Åkerbladh graduated Larhed and Associate Professor reactions towards the synthesis from the University of Gothen- Luke Odell at Uppsala University of heterocycles for which she re- burg with an MSc in Organic for her PhD studies focusing on ceived her PhD in 2017. and Medicinal Chemistry in the development of nongaseous 2010. She joined Professor Mats carbonylative multicomponent Luke Odell was born in sity under the guidance of 2009, he has been an Associate Tamworth, Australia in 1981. He Professor Adam McCluskey in Professor at Uppsala University graduated with an Honours BSc 2006 working on the synthesis and his research interests in- in Forensic Science from the of enzyme inhibitors. In 2006, clude metal catalysis, hetero- University of Newcastle, Austra- he took up a postdoctoral posi- cyclic chemistry, and medicinal This document was downloaded for personal use only. Unauthorized distribution is strictly prohibited. lia in 2002. He completed his tion with Professor Mats Larhed chemistry. PhD studies at the same univer- at Uppsala University. Since Mats Larhed received his PhD metal catalysis covers different in the development of PET in 1997 and became a full pro- types of palladium-catalyzed radiotracers, angiotensin II fessor in 2007. Dr Larhed’s main coupling reactions, gas-free car- ligands, and enzyme inhibitors research focus has been towards bonylations, and the for potential treatment of HIV, the development of fast, selec- development of environmental- Malaria, Alzheimers disease, and tive, and robust synthetic meth- ly benign chemical transforma- TB. ods for use in preparative tions. During the last ten years medicinal chemistry. His work in he has been increasingly engaged © Georg Thieme Verlag Stuttgart · New York — Synlett 2019, 30, 141–155 143 Syn lett L. Åkerbladh et al. Account 9-methylfluorene-9-carbonyl chloride (COgen). A special 2.3 Multicomponent Carbonylations two-chamber glassware system was developed to keep the carbonylation and the decarbonylation reaction mixtures A multicomponent reaction is defined as a reaction with separate, to avoid problems with incompatibility (Figure three or more reaction components that react to form a sin- 2).32 A similar approach was later described, in which a re- gle product that contains essentially all of the atoms of the action of silacarboxylic acid with a fluoride source liberated starting materials.44,45 The components may be separate CO.33 Both these methods allow the use of stoichiometric or molecular entities or they may be different functional substoichiometric amounts of CO as well as a possibility to groups in bifunctional reagents.44,46 As such, carbonylative introduce an isotopically labeled carbonyl group.32,33 coupling reactions, comprising the coupling of an electro- phile, CO, and a nucleophile, constitute a three-component reaction. However, carbonylation reactions with less than four components are not usually categorized as MCRs, be- cause the CO component is generally fixed, unless different carbon or oxygen isotopes are employed.47 Many well-known noncarbonylative MCRs, such as the Mannich,48 Strecker,49 Biginelli,50,51 Passerini,52,53 and Ugi54 reactions utilize carbonyl derivatives, for example in the form of aldehydes or ketones, to install additional carbons. The ability to incorporate one-carbon fragments by Pd(0)- catalyzed carbonylations from an additional source of orga- no(pseudo)halide starting materials is one of the reasons why carbonylation chemistry is such a powerful comple- ment to the field of MCRs. The advance of carbonylation chemistry and the development of numerous new methods6,10,55 has spurred an increased research interest in Figure 2 Two-Chamber vial after radical carbonylation reaction. Left- carbonylative MCRs.47,56 hand chamber (CCO) contains DBU/Mo(CO)6, right-hand chamber (Crxn) contains reactants.34 There are several advantages to carbonylative MCRs: (i) They are highly atom economical because nearly all atoms of the starting materials are incorporated into the product. Ex situ generation of carbon monoxide from solid CO (ii) The rapid assembly of simple starting materials to gen- sources, by using two-chamber glassware, has made it pos- erate cyclic and acyclic scaffolds with increased molecular sible to use various carbonylation reactions for small-scale complexity is readily achieved.
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