Development of a flow photochemical process for a π-Lewis acidic metal-catalyzed cyclization/radical addition sequence: in situ-generated 2-benzopyrylium as photoredox catalyst and reactive intermediate

• Masahiro Terada,
• Zen Iwasaki,
• Ryohei Yazaki,
• Shigenobu Umemiya and
• Jun Kikuchi

Beilstein J. Org. Chem. 2024, 20, 1973–1980, doi:10.3762/bjoc.20.173

• Abstract A flow photochemical reaction system for a π-Lewis acidic metal-catalyzed cyclization/radical addition sequence was developed, which utilizes in situ-generated 2-benzopyrylium intermediates as the photoredox catalyst and electrophilic substrates. The key 2-benzopyrylium intermediates were

• [26][27][28][29] is increased. Thus, the flow photochemical process is crucial and beneficial to product formation. Recently, we reported a sequential transformation consisting of a π-Lewis acidic metal-catalyzed cyclization [30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45] and

• improved the yield of 3t (78%), presumably because of the retardation of the desilylation process (from B to C in Scheme 1a). Conclusion We have demonstrated a flow reaction system for a π-Lewis acidic metal-catalyzed cyclization/photochemical radical addition sequence, affording, in most cases, the 1H

1,2-Difluoroethylene (HFO-1132): synthesis and chemistry

• Liubov V. Sokolenko,
• Taras M. Sokolenko and
• Yurii L. Yagupolskii

Beilstein J. Org. Chem. 2024, 20, 1955–1966, doi:10.3762/bjoc.20.171

• ], respectively, while reference [68] provides UV-spectral data of both isomers. 1H, 19F, and 13C NMR data [69][70] are given in Table 2. Chemistry of HFO-1132 Isomerization Iodine-catalyzed cis–trans isomerization of 1,2-difluoroethylene and corresponding equilibrium measurements were described in the 1960s [47

Negishi-coupling-enabled synthesis of α-heteroaryl-α-amino acid building blocks for DNA-encoded chemical library applications

• Matteo Gasparetto,
• Balázs Fődi and
• Gellért Sipos

Beilstein J. Org. Chem. 2024, 20, 1922–1932, doi:10.3762/bjoc.20.168

• ][28]. However, the selectivity of these photoredox reactions is driven by the structural properties of the heteroaromatic ring. During the preparation of this article, the Meggers group published an outstanding enantioselective iron-catalyzed α-amination pathway (Scheme 1b) [29]. The method is widely

• the blue region. This complex then accelerates the oxidative addition of the aryl halide to the metal, which is usually the rate-limiting step for palladium-catalyzed cross-couplings. Based on these results we decided to perform all Negishi reactions under blue light irradiation. With the optimized

Electrochemical radical cation aza-Wacker cyclizations

• Sota Adachi and
• Yohei Okada

Beilstein J. Org. Chem. 2024, 20, 1900–1905, doi:10.3762/bjoc.20.165

• photochemical reactions under acidic conditions, which were proposed to proceed via radical cations [20]. Since electrochemical and photochemical aza-Wacker cyclizations can offer ring systems that are difficult to construct through state-of-the-art palladium-catalyzed methods, the mechanistic understanding of

Access to 2-oxoazetidine-3-carboxylic acid derivatives via thermal microwave-assisted Wolff rearrangement of 3-diazotetramic acids in the presence of nucleophiles

• Ivan Lyutin,
• Vasilisa Krivovicheva,
• Grigory Kantin and
• Dmitry Dar’in

Beilstein J. Org. Chem. 2024, 20, 1894–1899, doi:10.3762/bjoc.20.164

• cyclization [15][16]. Additionally, the manganese(III)-promoted cyclization of N-alkenyl malonamides [17][18] and the Cu(I)-catalyzed reaction of propiolic acid derivatives with nitrones (Kinugasa reaction) [19][20][21] should also be mentioned, as well as intramolecular C–H insertion using

The Groebke–Blackburn–Bienaymé reaction in its maturity: innovation and improvements since its 21st birthday (2019–2023)

• Cristina Martini,
• Muhammad Idham Darussalam Mardjan and
• Andrea Basso

Beilstein J. Org. Chem. 2024, 20, 1839–1879, doi:10.3762/bjoc.20.162

• afforded a heterogeneous nanoreactor that could be employed in acid-catalyzed transformations. The GBB reactions were performed with 1 mol % catalyst at 35 °C under solvent-free conditions. A synergistic catalytic effect between polyoxometalate and LDH was evidenced by a higher catalytic activity of the

• also in the work reported by Shankar et al. [10], already mentioned in chapter 1. The authors established a solvent-catalyzed GBB-3CR to synthesize glycosylated imidazo[1,2-a]pyridines 33 starting from 1-formyl glycals 32; using HFIP as the solvent, the addition of any metal catalyst was not needed

• comprising a GBB-3CR and a palladium-catalyzed azide-isocyanide coupling to generate imidazo[1,2-a]pyridine-fused 1,3-benzodiazepines 85 (Scheme 27). The GBB reaction smoothly proceeded using 2-azidobenzaldehydes 83, 2-aminopyridines and isocyanides as the precursors. The in situ-generated azides 84 were

Chiral bifunctional sulfide-catalyzed enantioselective bromolactonizations of α- and β-substituted 5-hexenoic acids

• Sao Sumida,
• Ken Okuno,
• Taiki Mori,
• Yasuaki Furuya and
• Seiji Shirakawa

Beilstein J. Org. Chem. 2024, 20, 1794–1799, doi:10.3762/bjoc.20.158

• without substituents on the carbon–carbon double bond have remained a formidable challenge. To address this limitation, we report herein the asymmetric bromolactonization of 5-hexenoic acid derivatives catalyzed by a BINOL-derived chiral bifunctional sulfide. Keywords: asymmetric catalysis

• studies of chiral bifunctional sulfide-catalyzed bromolactonizations [26][27][28][29][30][31], mixed solvent systems were investigated. Among the examined solvent systems, a dichloromethane/toluene mixed solvent (3:1 ration) showed the best enantioselectivity (89:11 er). With the optimal catalyst (S)-1g

• products 3g and 3h were obtained with moderate to good levels of enantioselectivity. Unfortunately, the reaction with a simple 5-hexenoic acid 2i gave a δ-valerolactone 3i in low enantioselectivity. To expand the substrate scope of chiral bifunctional sulfide-catalyzed asymmetric bromolactonizations of 5

Syntheses and medicinal chemistry of spiro heterocyclic steroids

• Laura L. Romero-Hernández,
• Ana Isabel Ahuja-Casarín,
• Penélope Merino-Montiel,
• Sara Montiel-Smith,
• José Luis Vega-Báez and
• Jesús Sandoval-Ramírez

Beilstein J. Org. Chem. 2024, 20, 1713–1745, doi:10.3762/bjoc.20.152

• preparing spiro α-methylene-β-lactones from different steroidal propargylic alcohols [13]. The procedure involves a one-pot Pd-catalyzed cyclocarbonylation of alkynols using 5 mol % of Pd(CH3CN)2Cl2 as a catalyst precursor and 30 mol % of 2-(dibutyl)phosphine-1-(2,6-diisopropylphenyl)-1H-imidazole as

Chemo-enzymatic total synthesis: current approaches toward the integration of chemical and enzymatic transformations

• Ryo Tanifuji and
• Hiroki Oguri

Beilstein J. Org. Chem. 2024, 20, 1693–1712, doi:10.3762/bjoc.20.151

• pathway of brassicicenes in Pseudocercospora fijiensis is outlined based on an investigation by Oikawa and co-workers [23]. The biosynthesis begins with the conversion of farnesyl pyrophosphate (FPP) and isopentenyl pyrophosphate (IPP) to geranylgeranyl pyrophosphate (GGPP), catalyzed by the

• , introduce hydroxy groups at C8 and C16 to produce FD-8β,16-diol (7), and BscE-catalyzed O-methylation generates the putative intermediate 8. The subsequent oxidative allylic rearrangement (8→9), catalyzed by the nonheme iron(II) and 2-oxoglutarate (Fe(II)/2OG)-dependent dioxygenase BscD, was a key step

• , and subsequent reduction of the exomethylene at C11–C18 catalyzed by BscH yield brassicicene O (12). Renata and co-workers successfully accomplished the chemoenzymatic total syntheses of cotylenol (1) and nine brassicicenes (Scheme 3) [19]. In the cyclization phase, a suitably functionalized 5/8/5

pKalculator: A pK_a predictor for C–H bonds

• Rasmus M. Borup,
• Nicolai Ree and
• Jan H. Jensen

Beilstein J. Org. Chem. 2024, 20, 1614–1622, doi:10.3762/bjoc.20.144

• showed that our ML model is able to predict the reaction site for pKa-dependent reactions. Now, we test the ML model on a more complex reaction type, namely, borylation reactions. Caldeweyher et al. [45] presented a workflow to predict the iridium-catalyzed borylation site of aryl C–H bonds (SoBo) [45

Generation of multimillion chemical space based on the parallel Groebke–Blackburn–Bienaymé reaction

• Evgen V. Govor,
• Vasyl Naumchyk,
• Ihor Nestorak,
• Dmytro S. Radchenko,
• Dmytro Dudenko,
• Yurii S. Moroz,
• Olexiy D. Kachkovsky and
• Oleksandr O. Grygorenko

Beilstein J. Org. Chem. 2024, 20, 1604–1613, doi:10.3762/bjoc.20.143

• , is a powerful tool for the combinatorial synthesis of compound libraries. We have shown that the Sc(OTf)3-catalyzed version of the reaction has a wide substrate applicability and established some limitations under the parallel synthesis conditions. In particular, while the method was applicable to a

Primary amine-catalyzed enantioselective 1,4-Michael addition reaction of pyrazolin-5-ones to α,β-unsaturated ketones

• Pooja Goyal,
• Akhil K. Dubey,
• Raghunath Chowdhury and
• Amey Wadawale

Beilstein J. Org. Chem. 2024, 20, 1518–1526, doi:10.3762/bjoc.20.136

• 10.3762/bjoc.20.136 Abstract The enantioselective 1,4-addition reaction of pyrazolin-5-ones to α,β-unsaturated ketones catalyzed by a cinchona alkaloid-derived primary amine–Brønsted acid composite is reported. Both enantiomers of the anticipated pyrazole derivatives were obtained in good to excellent

• disclosed organocatalyzed [5 + 1] double Michael additions between pyrazolones and dienones (Scheme 1b) [23]. Very recently, the Chimni group reported a cinchona-derived squaramide-catalyzed 1,4-Michael addition reaction of pyrazolin-5-ones with 2-enoylpyridines (Scheme 1c) [24]. Recently, we developed an

Tetrabutylammonium iodide-catalyzed oxidative α-azidation of β-ketocarbonyl compounds using sodium azide

• Christopher Mairhofer,
• David Naderer and
• Mario Waser

Beilstein J. Org. Chem. 2024, 20, 1510–1517, doi:10.3762/bjoc.20.135

• peroxide catalyzed by tetrabutylammonium iodide (TBAI). By utilizing these readily available bulk chemicals a variety of cyclic β-ketocarbonyl derivatives can be efficiently α-azidated under operationally simple conditions. Control experiments support a mechanistic scenario involving in situ formation of

• an ammonium hypoiodite species which first facilitates the α-iodination of the pronucleophile, followed by a phase-transfer-catalyzed nucleophilic substitution by the azide. Furthermore, we also show that an analogous α-nitration by using NaNO2 under otherwise identical conditions is possible as well

• conditions are best-suited. We have recently established the use of dibenzoyl peroxide (DBPO) as a very powerful oxidant for oxidative heterofunctionalization reactions using simple nucleophilic inorganic salts as heteroatom transfer reagents [39][41]. This was successfully demonstrated for the non-catalyzed

Towards an asymmetric β-selective addition of azlactones to allenoates

• Behzad Nasiri,
• Ghaffar Pasdar,
• Paul Zebrowski,
• Katharina Röser,
• David Naderer and
• Mario Waser

Beilstein J. Org. Chem. 2024, 20, 1504–1509, doi:10.3762/bjoc.20.134

• thus wondering if we could extend this ammonium salt-catalyzed β-selective allenoate functionalization strategy to other amino acid classes. Azlactones 1 have previously been used for γ-selective additions to allenoates under chiral phosphine catalysis [28]. In addition, glycine Schiff base derivatives

• transformation under asymmetric ammonium salt catalysis [35][36][37][38] and the results of these investigations are outlined in this contribution (Scheme 1C). Results and Discussion We started our investigations by testing the quaternary ammonium salt-catalyzed addition of azlactone 1a to allenoate 3a (Table 1

• ammonium salt-catalyzed β-selective addition of compounds 2 to allenoates 3 (B), and the herein investigated β-selective addition of azlactones 1 to allenoates 3 (C). Application scope (conditions as detailed in Table 1, entry 13). Azlactone opening reactions. Optimization of the addition of azlactone 1a

Electrophotochemical metal-catalyzed synthesis of alkylnitriles from simple aliphatic carboxylic acids

• Yukang Wang,
• Yan Yao and
• Niankai Fu

Beilstein J. Org. Chem. 2024, 20, 1497–1503, doi:10.3762/bjoc.20.133

• .20.133 Abstract We report a practical and sustainable electrophotochemical metal-catalyzed protocol for decarboxylative cyanation of simple aliphatic carboxylic acids. This environmentally friendly method features easy availability of substrates, broad functional group compatibility, and directly

• decarboxylative cyanation of arylacetic acids [35][36][37]. Considering the widespread availability of aliphatic carboxylic acids and the significant synthetic and medicinal importance of alkylnitriles, we envisioned that the electrophotochemical Ce-catalyzed radical decarboxylation of alkyl carboxylic acids in

• combination with electrochemical copper catalysis might allow rapid access to alkylnitriles in a generic fashion (Figure 1C). Herein, we disclose the successful implementation of this strategy and present a mild, practical, and broadly applicable electrophotochemical metal-catalyzed protocol for the direct

Photoswitchable glycoligands targeting Pseudomonas aeruginosa LecA

• Yu Fan,
• Ahmed El Rhaz,
• Stéphane Maisonneuve,
• Emilie Gillon,
• Maha Fatthalla,
• Franck Le Bideau,
• Guillaume Laurent,
• Samir Messaoudi,
• Anne Imberty and
• Juan Xie

Beilstein J. Org. Chem. 2024, 20, 1486–1496, doi:10.3762/bjoc.20.132

• the o,o’-bis-substituted derivative failed. For the β-S-galactosyl azobenzene derivatives which are accessible by our previously reported Pd-catalyzed cross-coupling methodology between glycosyl thiols and iodoaryl partners [30][38], the required p-, m- or o-iodo-p’-hydroxyazobenzenes 12, 17, and 21

• were prepared by the diazonium coupling method according to a reported procedure [39][40]. Then the coupling with tetra-O-acetylated β-galactosylthiol 13 catalyzed by Xantphos Pd-G3 [38] as precatalyst followed by post-functionalization furnished the desired β-S-galactosyl azobenzenes 3, 4, and 5 in

Bioinformatic prediction of the stereoselectivity of modular polyketide synthase: an update of the sequence motifs in ketoreductase domain

• Changjun Xiang,
• Shunyu Yao,
• Ruoyu Wang and
• Lihan Zhang

Beilstein J. Org. Chem. 2024, 20, 1476–1485, doi:10.3762/bjoc.20.131

• either A2- or B2-KRs, but are likely to contain mutations in NADPH binding site [31]. Sequence logo analysis of KRC from γ- and δ-modules In the actinobacterial γ- and δ-modules, the stereochemical outcome of a KR is obscured by further dehydration catalyzed by DH. The dehydration mechanism by DH has

Synthesis of 2-benzyl N-substituted anilines via imine condensation–isoaromatization of (E)-2-arylidene-3-cyclohexenones and primary amines

• Lu Li,
• Na Li,
• Xiao-Tian Mo,
• Ming-Wei Yuan,
• Lin Jiang and
• Ming-Long Yuan

Beilstein J. Org. Chem. 2024, 20, 1468–1475, doi:10.3762/bjoc.20.130

• are not always readily accessible. Typically, the preparation methods involve SNAr reactions with N-centered nucleophiles [5], nitroarene reduction [6] and transition metal (e.g., Pd, Cu)-catalyzed C–N cross coupling of aryl halides, aryl sulfonates or arylboronic acid reagents with ammonia or NH

• –dehydrogenative aromatization strategy with amines as nucleophiles [11][12]. For instance, the groups of Deng and Li reported the Pd catalyzed oxidative coupling of 2-cyclohexenones with amines [13]. Later, the same group demonstrated the direct amination of phenols by reductive coupling of in situ generated 2

• -cyclohexenones with nucleophilic nitrogen sources like ammonia, amines and hydrazine [14]. The reactions were regarded as via simple nucleophilic addition along with Pd-catalyzed dehydrogenative aromatization in these elegant works (Scheme 1, (1)). The Semmler–Wolff reaction is often implemented in the synthesis

Challenge N- versus O-six-membered annulation: FeCl₃-catalyzed synthesis of heterocyclic N,O-aminals

• Giacomo Mari,
• Lucia De Crescentini,
• Gianfranco Favi,
• Fabio Mantellini,
• Diego Olivieri and
• Stefania Santeusanio

Beilstein J. Org. Chem. 2024, 20, 1412–1420, doi:10.3762/bjoc.20.123

• intermediates through selective FeCl3-catalyzed intramolecular N-annulation. Keywords: α-aminoacetals; fused-ring systems; heterocyclic hemiaminals; heterocyclic N,O-aminals; multicomponent reactions; Introduction N-Fused heterocycles are ubiquitous within crucial molecules, including biologically active

• to afford, by a chemospecific Lewis acid-catalyzed ring-closure protocol, valuable heterocyclic N,O-aminals (Scheme 1). Results and Discussion Since the direct functionalization of N-heterocycles offers an attractive entry to important molecular targets that might otherwise require lengthy synthetic

• transformations in a single reactor, reducing the number of steps and the amount of waste with consequent benefits of cost and environmental impact [42][43]. Representative examples of relevant N-fused heterocycles. Different acid-catalyzed six-membered ring cyclizations. Substrate scope for the assembly of

Hypervalent iodine-catalyzed amide and alkene coupling enabled by lithium salt activation

• Akanksha Chhikara,
• Fan Wu,
• Navdeep Kaur,
• Prabagar Baskaran,
• Alex M. Nguyen,
• Zhichang Yin,
• Anthony H. Pham and
• Wei Li

Beilstein J. Org. Chem. 2024, 20, 1405–1411, doi:10.3762/bjoc.20.122

• catalysis, which often involves the catalytic use of an iodoarene with stoichiometric oxidants such as MCPBA, Selectfluor, etc. [18][19][20]. Earlier and recent hypervalent iodine-catalyzed olefin halofunctionalizations by several groups have predicated on the use of intramolecular olefin substrates

• tethered with a nucleophile to avoid the lack of regiochemical additions (Scheme 1a) [21][22][23][24][25][26][27][28]. Intermolecular hypervalent iodine-catalyzed olefin difunctionalizations have been realized for olefin dihalogenation, dioxygenation and diamination reactions, where often the same type of

• hypervalent iodine catalyst. The cationic hypervalent iodine catalyst could then activate the olefin to allow the addition of bifunctional nucleophiles such as an amide to achieve an overall olefin oxyamination process. We have previously reported a series of iodide-catalyzed processes, in which the

Synthesis of substituted triazole–pyrazole hybrids using triazenylpyrazole precursors

• Simone Gräßle,
• Laura Holzhauer,
• Nicolai Wippert,
• Olaf Fuhr,
• Martin Nieger,
• Nicole Jung and
• Stefan Bräse

Beilstein J. Org. Chem. 2024, 20, 1396–1404, doi:10.3762/bjoc.20.121

• the triazole unit via a copper-catalyzed azide–alkyne cycloaddition. The developed methodology was used to synthesize a library of over fifty new multi-substituted pyrazole–triazole hybrids. We also demonstrate a one-pot strategy that renders the isolation of potentially hazardous azides obsolete. In

• cholerae [13], show antimicrobial properties [14], and can act as P2X7 antagonists, a receptor involved in neuroinflammation and depression [15]. Pyrazolyltriazoles are most easily obtained via the copper-catalyzed azide–alkyne cycloaddition (CuAAC) from pyrazolyl azides (7 and 8). These are usually

• aromatic and aliphatic alkynes 20a–h in a copper-catalyzed azide–alkyne cycloaddition (CuAAC). All attempted reactions could be conducted under standard conditions using copper sulfate and sodium ascorbate in THF/water (depicted in Scheme 3 and Figure 2). For selected derivatives, 21sd and 21vg, crystals

Synthetic applications of the Cannizzaro reaction

• Bhaskar Chatterjee,
• Dhananjoy Mondal and
• Smritilekha Bera

Beilstein J. Org. Chem. 2024, 20, 1376–1395, doi:10.3762/bjoc.20.120

• different phase-transfer reagents and catalysts such as benzyltriethylammonium chloride, tetrabutylammonium bromide and many others have had profound impacts on the Cannizzaro reaction. Entezari and Shameli [27] studied the effect of an ultrasonic wave on the Cannizzaro reaction catalyzed by a phase

• where other methods of oxidation or reduction might be challenging or impractical. The present discussion focuses on some recent synthetic advances and their application in biologically active compounds. Lewis acid-catalyzed intramolecular Cannizzaro reaction Wang et al. [73] depicted a highly

• oxidation of the aryl methyl ketones 5 to the corresponding aryl glyoxal with concomitant rearrangement of the aryl glyoxal to the target α-hydroxycarboxylic acid derivatives 6, catalyzed by Yb(OTf)3. The simple process reflects the generality of the methodology with yields ranging from 78–99% as

Generation of alkyl and acyl radicals by visible-light photoredox catalysis: direct activation of C–O bonds in organic transformations

• Mithu Roy,
• Bitan Sardar,
• Itu Mallick and
• Dipankar Srimani

Beilstein J. Org. Chem. 2024, 20, 1348–1375, doi:10.3762/bjoc.20.119

• [28] introduced the photoredox-catalyzed hydroacylation of styrene derivatives via deoxygenation of challenging aliphatic carboxylic acids (Scheme 1). The deoxygenation was promoted by phosphine reagents to form acyl radicals. The acyl radicals reacted with the C=C bond and formed the expected product

• prefunctionalized alcohols that are used under visible-light photoredox conditions to generate alkyl radicals by homolysis of C–O bonds. Thiocarbonyl: In 2014, Ollivier and co-workers [43] demonstrated visible-light-mediated iridium-catalyzed reduction of thiocarbonyl derivatives derived from alcohols. The

• co-workers [46] utilized oxalates as activating groups for alcohols. Alkyl oxalates were effectively converted into useful radicals, catalyzed by an iridium complex under visible-light photoredox conditions (Scheme 9). This new approach does not require any sacrificial use of reductants or oxidants

Rhodium-catalyzed homo-coupling reaction of aryl Grignard reagents and its application for the synthesis of an integrin inhibitor

• Kazuyuki Sato,
• Satoki Teranishi,
• Atsushi Sakaue,
• Yukiko Karuo,
• Atsushi Tarui,
• Kentaro Kawai,
• Hiroyuki Takeda,
• Tatsuo Kinashi and
• Masaaki Omote

Beilstein J. Org. Chem. 2024, 20, 1341–1347, doi:10.3762/bjoc.20.118

• 10.3762/bjoc.20.118 Abstract A novel Rh-catalyzed one-pot homo-coupling reaction of aryl Grignard reagents was achieved. The reaction with bromobenzenes having an electron-donating group or a halogen substituent gave the corresponding homo-coupling products in good yields, although the reaction using

• benign synthetic applications [14][15][16][17][18]. We have successfully achieved various reactions using a Rh complex easily derived from dialkylzinc (R2Zn) and RhCl(PPh3)3 [19][20]. Additionally, in the related study, we also reported a new Rh-catalyzed C(sp3)–C(sp3) homo-coupling reaction of benzyl

• halides, which involved a rhodium-bis(benzyl) complex (Scheme 2) [21]. Following these outcomes, as part of a research program aimed at a wide range of Rh-catalyzed C–C bond-formation reactions, in this paper, we report a Rh-catalyzed Ullmann-type homo-coupling reaction of aryl Grignard reagents. Results

Transition-metal-catalyst-free electroreductive alkene hydroarylation with aryl halides under visible-light irradiation

• Kosuke Yamamoto,
• Kazuhisa Arita,
• Masami Kuriyama and
• Osamu Onomura

Beilstein J. Org. Chem. 2024, 20, 1327–1333, doi:10.3762/bjoc.20.116

• versatile building blocks in organic syntheses. To achieve this transformation with high efficiency and predictable regioselectivity, numerous efforts have been made to develop transition-metal-catalyzed reactions based on a C–H activation strategy [1][2][3][4] or the reductive coupling of aryl halides with