Palladium-catalyzed dual C–H or N–H functionalization of unfunctionalized indole derivatives with alkenes and arenes

• Gianluigi Broggini,
• Egle M. Beccalli,
• Andrea Fasana and
• Silvia Gazzola

Beilstein J. Org. Chem. 2012, 8, 1730–1746, doi:10.3762/bjoc.8.198

• , exploiting the nucleophilicity of the C-2 and C-3 indolyl positions and the subsequent addition of carbon monoxide and the proper alcohol, a broad range of alkoxycarbonyl-substituted indoles fused to various sizes of rings has been achieved under mild conditions. A similar intermolecular version of the

• . The subsequent transfer of carbon monoxide with stereochemical retention determines the generation of the σ-acyl-palladium complex XVIII, which in turn is converted in the final cis-substituted tetrahydrocarbazole by methanolysis giving the carboxylation step. Again, the released Pd(0) species

Amines as key building blocks in Pd-assisted multicomponent processes

• Didier Bouyssi,
• Nuno Monteiro and
• Geneviève Balme

Beilstein J. Org. Chem. 2011, 7, 1387–1406, doi:10.3762/bjoc.7.163

• , thioether and ester groups, although enolizable alkylimines were not suitable under these conditions (Scheme 1). Replacement of the acid chloride with a chloroformate under 1 atmosphere of carbon monoxide as a fourth component led to ketocarbamates 3 in a single operation through a carbonylative coupling [3

• , based on a similar strategy, through the assembly of four components, namely, imines, acid chloride and carbon monoxide. The process is thought to begin with formation of a münchnone 5, resulting from oxidative addition of an acyliminium species to Pd(0), followed by CO insertion and β-hydride

• different approach to α,β-alkynyl ketone derivatives as pyrazole precursors. They established a four-component domino process combining various organic halides, terminal alkynes, hydrazines, and carbon monoxide at room temperature. In this case, all components are mixed at the very beginning of the process

Koch–Haaf reaction of adamantanols in an acid-tolerant hastelloy-made microreactor

• Takahide Fukuyama,
• Yu Mukai and
• Ilhyong Ryu

Beilstein J. Org. Chem. 2011, 7, 1288–1293, doi:10.3762/bjoc.7.149

• practical organic syntheses using flow microreactors, and we have reported thus far examples of Pd-catalyzed coupling reactions [11][12][13], radical reactions [14][15][16], and photoreactions [17][18][19][20][21]. Carbonylation reactions are a powerful tool for the introduction of carbon monoxide into

Rh(I)-catalyzed intramolecular [2 + 2 + 1] cycloaddition of allenenes: Construction of bicyclo[4.3.0]nonenones with an angular methyl group and tricyclo[6.4.0.0^1,5]dodecenone

• Fuyuhiko Inagaki,
• Naoya Itoh,
• Yujiro Hayashi,
• Yumi Matsui and
• Chisato Mukai

Beilstein J. Org. Chem. 2011, 7, 404–409, doi:10.3762/bjoc.7.52

• ] cycloaddition of three components, the alkyne π-bond, the alkene π-bond and carbon monoxide (CO), for producing cyclopentenone derivatives. The intramolecular PKR [3][4][5][6][7][8][9] provides a powerful method for the construction of bicyclo[3.3.0]oct-1-en-3-one and bicyclo[4.3.0]non-1(9)-en-8-one frameworks

Molecular rearrangements of superelectrophiles

• Douglas A. Klumpp

Beilstein J. Org. Chem. 2011, 7, 346–363, doi:10.3762/bjoc.7.45

• ) yields superelectrophile 70 by migration of the methyl group. Protolysis also occurs at the methine position (72) which leads directly to superelectrophile 73. Ions 70 and 73 react with carbon monoxide to give products 66 and 65, respectively, on aqueous workup. The major product 67 evidently arises from

• , the monocation 96 undergoes a hydride shift to form the carboxonium ion 97 which leads to ketone 98 on deprotonation. Methyl isopropyl ketone (98) is known [32] to be an excellent gasoline oxygenate. Since pivaldehyde can be made from carbon monoxide and isobutane (in superacid), this

• superelectrophilic rearrangement may have significant commercial value. Other isoalkanes have shown similar chemistry. For example, 3-methylpentane reacts with carbon monoxide to give the isomeric C7 ketones. A retro-pinacol rearrangement is triggered by the superelectrophilic carboxonium 100 and subsequent

Miniemulsion polymerization as a versatile tool for the synthesis of functionalized polymers

• Daniel Crespy and
• Katharina Landfester

Beilstein J. Org. Chem. 2010, 6, 1132–1148, doi:10.3762/bjoc.6.130

• -chelated Ni(II) catalyst to obtain dispersions with up to 30% solid content [64]. The copolymerization of carbon monoxide with ethylene or 1-olefins with catalysts formed in situ from palladium(II) complexes gave aliphatic polyketones [65]. The catalyst activity was slightly higher as compared to non

Radical carbonylations using a continuous microflow system

• Takahide Fukuyama,
• Md. Taifur Rahman,
• Naoya Kamata and
• Ilhyong Ryu

Beilstein J. Org. Chem. 2009, 5, No. 34, doi:10.3762/bjoc.5.34

• pressurized carbon monoxide gas. Good to excellent yields of carbonylated products were obtained via radical formylation, carbonylative cyclization and three-component coupling reactions, using tributyltin hydride or TTMSS as a radical mediator. Keywords: continuous flow system; microreactor; radical

• yields of the desired products. Carbon monoxide is an important feedstock and our group has actively pursued carbonylation reactions [14][15][16][17]. Thermally induced radical carbonylations using tin hydride usually require pressurized CO conditions to ensure that the concentration of CO around the

Mitomycins syntheses: a recent update

• Jean-Christophe Andrez

Beilstein J. Org. Chem. 2009, 5, No. 33, doi:10.3762/bjoc.5.33

Transition- metal/Lewis acid free synthesis of acyl benzothiophenes via C-C bond forming reaction

• Sarbani Pal,
• Mohammad Ashrafuddin Khan,
• P. Bindu and
• P. K. Dubey

Beilstein J. Org. Chem. 2007, 3, No. 35, doi:10.1186/1860-5397-3-35

• an expensive transition metal catalyst along with toxic carbon monoxide gas[13] or unstable diazo compounds,[18] or pyrophoric BuLi,[19][20] or a multistep synthesis of starting material.[14] The simplest and straightforward method for the synthesis of acyl benzothiophenes appeared to be the Friedel

Flexible synthetic routes to poison- frog alkaloids of the 5,8-disubstituted indolizidine- class I: synthesis of common lactam chiral building blocks and application to the synthesis of (-)-203A, (-)-205A, and (-)-219F

• Naoki Toyooka,
• Dejun Zhou,
• Hideo Nemoto,
• H. Martin Garraffo,
• Thomas F. Spande and
• John W. Daly

Beilstein J. Org. Chem. 2007, 3, No. 29, doi:10.1186/1860-5397-3-29

• enoltriflate 5 in good yield. The palladium-catalyzed carbon monoxide insertion reaction [17] in the presence of MeOH afforded the enaminoester 6. The key Michael-type conjugate addition reaction of 6 with lithium dimethylcuprate or divinylcuprate proceeded smoothly to provide the trisubstituted piperidines (7

The use of silicon- based tethers for the Pauson- Khand reaction

• Adrian P. Dobbs,
• Ian J. Miller and
• Saša Martinović

Beilstein J. Org. Chem. 2007, 3, No. 21, doi:10.1186/1860-5397-3-21

• obtained, only the cycloisomerisation products predicted by Saigo.[7] Repeating the reactions under 1 atm pressure of carbon monoxide also gave only the isomerisation products, albeit in higher yields and more rapidly. In every example, the main product, accounting for the bulk of the mass balance, were