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Palladium and Copper Catalyzed Sonogashira Cross Coupling an Excellent Methodology for C-C Bond Formation Over 17 Years: a Review

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Palladium and Copper Catalyzed Sonogashira Cross Coupling an Excellent Methodology for C-C Bond Formation Over 17 Years: a Review catalysts Review Palladium and Copper Catalyzed Sonogashira cross Coupling an Excellent Methodology for C-C Bond Formation over 17 Years: A Review Iram Kanwal 1, Aqsa Mujahid 1, Nasir Rasool 1,*, Komal Rizwan 1,2, Ayesha Malik 1, Gulraiz Ahmad 1, Syed Adnan Ali Shah 3,4, Umer Rashid 5,* and Nadiah Mad Nasir 6 1 Department of Chemistry, Government College University Faisalabad, Punjab 38000, Pakistan; [email protected] (I.K.); [email protected] (A.M.); [email protected] (K.R.); [email protected] (A.M.); [email protected] (G.A.) 2 Department of Chemistry, University of Sahiwal, Sahiwal 57000, Pakistan 3 Faculty of Pharmacy, Universiti Teknologi MARA Cawangan Selangor Kampus Puncak Alam, Bandar Puncak Alam 42300, Selangor D. E., Malaysia; [email protected] 4 Atta-ur-Rahman Institute for Natural Products Discovery (AuRIns), Universiti Teknologi MARA Cawangan Selangor Kampus Puncak Alam, Bandar Puncak Alam 42300, Selangor D. E., Malaysia 5 Institute of Advanced Technology, Universiti Putra Malaysia, Serdang 43400 UPM, Selangor, Malaysia 6 Department of Chemistry, Universiti Putra Malaysia, Serdang 43400 UPM, Selangor, Malaysia; [email protected] * Correspondence: [email protected] (N.R.); [email protected] or [email protected] (U.R.); Tel.: +92-332-7491790 (N.R.); +60-3-9769-7393 (U.R.); Fax: +92-41-9201032 (N.R.); +60-3-9769-7006 (U.R.) Received: 12 December 2019; Accepted: 14 January 2020; Published: 20 April 2020 Abstract: Sonogashira coupling involves coupling of vinyl/aryl halides with terminal acetylenes catalyzed by transition metals, especially palladium and copper. This is a well known reaction in organic synthesis and plays a role in sp2-sp C-C bond formations. This cross coupling was used in synthesis of natural products, biologically active molecules, heterocycles, dendrimers, conjugated polymers and organic complexes. This review paper focuses on developments in the palladium and copper catalyzed Sonogashira cross coupling achieved in recent years concerning substrates, different catalyst systems and reaction conditions. Keywords: cross coupling; copper; palladium; transition; Sonogashira 1. Introduction The transition metal catalyzed cross-coupling reactions have played an important role in the field of organic synthesis [1,2]. Among them, the palladium catalyzed sp2-sp couplings between aryl or alkenyl halides or triflates and terminal alkynes in presence or absence of Copper (I) cocatalyst has become the most important method to prepare aryl-alkynes and conjugated enynes (Figure1), which are precursors for pharmaceuticals, natural products and organic materials and this type of coupling commonly known as Sonogashira coupling [3–5]. This reaction was named after the scientists Sonogashira, Tohda, and Hagihara in 1975. Catalysts 2020, 10, 443; doi:10.3390/catal10040443 www.mdpi.com/journal/catalysts Catalysts 2020, 10, 443 2 of 48 Catalysts 2020, 10, x FOR PEER REVIEW 2 of 48 Figure 1. General schematic presentationFigure of 1. Sonogashira Cross Coupling reaction. This research came after Cassar [[6]6] and DieckDieck and Heck [[7]7] discloseddisclosed that it waswas possiblepossible to performperform thisthis coupling coupling only only under under palladium palladium catalyst catalyst at high at temperatures. high temperatures. Sonogashira Sonogashira and Hagihara and reportedHagihara that reported addition that of addition catalytic of amount catalytic of Copper amount (I) of iodide Copper accelerates (I) iodide the accelerates C-C bond the formations C-C bond at roomformations temperature at room [ 8temperature]. However, [8]. addition However, of copper addition has of many copper benefits, has many but benefits, it has some but drawbacksit has some associateddrawbacks withassociated it, the with main it, one the beingmain theone necessitybeing the ofnecessity avoiding of theavoiding presence the presence of oxygen of in oxygen order toin blockorder theto block undesirable the undesirable formation formation of alkyne homocouplingof alkyne homocoupling through a copper-mediatedthrough a copper-mediated Hay/Glaser reactionHay/Glaser [9] alongreaction with [9] the along main productwith the and main diffi productculty in recoveryand difficulty of reagents. in recovery To overcome of reagents. this issue, To eliminationovercome this of theissue, copper elimination was a solution, of the copper so perhaps was a insolution, this case so the perhaps process in maythis case be called the process copper-free may Sonogashirabe called copper-free reaction, orSonogashira Heck-Cassar reaction, reaction, or Heck Heck-Cassar alkynylation reaction, or perhaps Heck Sonogashira-Heck-Cassar alkynylation or perhaps coupling.Sonogashira-Heck-Cassar Significant efforts coupling. were made Significant to develop effort the couplings were made reaction to develop and enhancement the coupling of reactivity reaction ofand catalytic enhancement system inof absencereactivity of copperof catalytic sources. system The in copper absence free of coupling copper process sources. involves The copper the use free of excesscoupling amine process which involves often the acts use as of asolvent, excess amine but the whic environmentalh often acts as and a solvent, economic but the advantages environmental of the methodologyand economic end advantages here. Thus, of ethefforts methodology were made toen developd here. SonogashiraThus, efforts cross-coupling were made to reaction develop in absenceSonogashira of both cross-coupling copper and amines reaction [10 in]. absence In the Sonogashira of both copper process, and di aminesfferent substrates[10]. In the have Sonogashira different reactivitiesprocess, different as sp2 speciessubstrates reactivity have different order was reactiviti found toes beas sp2 vinyl species iodide reactivity> vinyl triflate order >wasvinyl found bromide to be >vinylvinyl iodide chloride > vinyl> aryl triflate iodide > vinyl> aryl bromide triflate > vinylaryl bromide chloride >> aryl chloride.iodide > aryl In organic triflate > halides, aryl bromide which are> aryl activated chloride. (electron-poor), In organic halides, the situation which are is even activated more (electron-poor), promising [11]. the The situation products is obtainedeven more in Sonogashirapromising [11]. reaction The haveproducts various obtained applications in Sonogash in theira diverse reaction areas have of chemistry, various applications such as electronics, in the dyes,diverse polymers, areas of sensors,chemistry, natural such products as electronics, and in dyes, synthesis polymers, of heterocycles. sensors, natural Remarkable products research and onin thissynthesis topic of has heterocycles. been going Remarkable on for decades research to search on this for topic more has convenient been going reaction on for decades conditions to search and a better,for more effi convenientcient catalytic reaction system conditions and for synthesis and a bette ofr, promising efficient catalytic compounds. system This and review for synthesis covers the of developmentspromising compounds. in the Sonogashira This review cross-coupling covers the reaction, developments as well asin applicationsthe Sonogashira of this cross-coupling methodology fromreaction, 2002 as to well 2018. as applications of this methodology from 2002 to 2018. 2. Literature Review The palladiumpalladium catalyzed cross couplingcoupling betweenbetween carboncarbon halideshalides andand terminalterminal acetylenesacetylenes havehave been reported by variousvarious researchresearch groupsgroups [[12].12]. TheseThese cross couplings have used the formation of a carbon-carbon bond.bond. The copper as co-catalyst with palladium complexes were used for Sonogashira cross couplingcoupling [[13].13]. The Sonogashira cross coupling was also used for the preparation of compounds whichwhich areare pharmacologicallypharmacologically andand biologicallybiologically active.active. In this cross coupling, the various ligands with palladiumpalladium andand coppercopper co-catalystco-catalyst havehave beenbeen usedused byby variousvarious researchresearch groups.groups. 2.1. In 2002 2.1. In 2002 The Sonogashira cross coupling was used for synthesizes of different organic compounds The Sonogashira cross coupling was used for synthesizes of different organic compounds which which are used as precursors for biologically active molecules. Earlier, the triple bond in C-9 and are used as precursors for biologically active molecules. Earlier, the triple bond in C-9 and C-10 of C-10 of Stereo-selective 9,10-didehydro retinoic acids 4 were formed “by Witting reaction” and by Stereo-selective 9,10-didehydro retinoic acids 4 were formed “by Witting reaction” and by addition addition reaction of 4-methyl-pyrylium tetra-fluoro-borate on appropriate substrate, but protection reaction of 4-methyl-pyrylium tetra-fluoro-borate on appropriate substrate, but protection and de- and de-protection steps were used in these reactions. In 2002, the Sonogashira cross coupling was protection steps were used in these reactions. In 2002, the Sonogashira cross coupling was used by used by Abarbri and co-workers for the synthesis of 4 Stereo-selective 9,10-didehydro retinoic acids Abarbri and co-workers for the synthesis of 4 Stereo-selective 9,10-didehydro retinoic acids without without protection and de-protection of carboxylic acid. The dienyoic acid 3 was also synthesized via protection and de-protection of carboxylic acid. The dienyoic acid 3 was also synthesized via
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