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Search for "Stille reaction" in Full Text gives 11 result(s) in Beilstein Journal of Organic Chemistry.
Non-noble metal-catalyzed cross-dehydrogenation coupling (CDC) involving ether α-C(sp3)–H to construct C–C bonds
- Hui Yu and
- Feng Xu
Beilstein J. Org. Chem. 2023, 19, 1259–1288, doi:10.3762/bjoc.19.94
- Negishi reaction (Zn) [1], Stille reaction (Sn) [2], Kumada reaction (Mg) [3], and Suzuki reaction (Pd) [4] (Scheme 1a). However, these coupling reactions involve a metal exchange step that generates a considerable amount of reaction waste, such as metal salts, which are not environmentally friendly. To
Graphical Abstract
Scheme 1: Research progress of coupling reactions and active compounds containing α-C(sp3)-functionalized eth...
Scheme 2: Transition-metal-catalyzed CDC pathways.
Scheme 3: CDC of active methylene compounds in the α-C(sp3) position of ethers.
Scheme 4: InCl3/Cu(OTf)2/NHPI co-catalyzed CDC reaction.
Scheme 5: CDC of cyclic benzyl ethers with aldehydes.
Scheme 6: Cu-catalyzed CDC of (a) unactivated C(sp3)–H ethers with simple ketones and (b) double C(sp3)−H fun...
Scheme 7: Cu-catalyzed CDC of C(sp3)–H/C(sp3)–H bonds.
Scheme 8: Cu-catalyzed synthesis of chiral 2-substituted tetrahydropyrans.
Scheme 9: CDC of thiazole with cyclic ethers.
Scheme 10: Cu(I)-catalyzed oxidative alkenylation of simple ethers.
Scheme 11: Cross-dehydrogenation coupling of isochroman C(sp3)–H bonds with anisole C(sp2)–H bonds.
Scheme 12: Pd(OAc)2/Cu(OTf)2-catalyzed arylation of α-C(sp3)–H bonds of ethers.
Scheme 13: Cu-catalyzed C(sp3)–H/C(sp2)–H activation strategies to construct C(sp3)–C(sp2) bonds.
Scheme 14: Cu(I)-catalyzed C(sp2)–H alkylation.
Scheme 15: Cu-catalyzed C(sp3)–H/C(sp)–H activation to construct C(sp3)–C(sp) bonds (H2BIP: 2,6-bis(benzimidaz...
Scheme 16: Fe-catalyzed CDC reaction pathways.
Scheme 17: Fe2(CO)9-catalyzed functionalization of C–H bonds.
Scheme 18: Ligand-promoted Fe-catalyzed CDC reaction of N-methylaniline with ethers.
Scheme 19: Fe-catalyzed CDC of C(sp3)–H/C(sp3)–H bonds.
Scheme 20: Fe-catalyzed hydroalkylation of α,β-unsaturated ketones with ethers.
Scheme 21: Solvent-free Fe(NO3)3-catalyzed CDC of C(sp3)–H/C(sp2)–H bonds.
Scheme 22: Alkylation of disulfide compounds to afford tetrasubstituted alkenes.
Scheme 23: Fe-catalyzed formation of 1,1-bis-indolylmethane derivatives.
Scheme 24: Alkylation of coumarins and flavonoids.
Scheme 25: Direct CDC α-arylation of azoles with ethers.
Scheme 26: CDC of terminal alkynes with C(sp3)–H bonds adjacent to oxygen, sulfur or nitrogen atoms.
Scheme 27: Alkylation of terminal alkynes.
Scheme 28: Co-catalyzed functionalization of glycine esters.
Scheme 29: Co-catalyzed construction of C(sp2)–C(sp3) bonds.
Scheme 30: Co-catalyzed CDC of imidazo[1,2-a]pyridines with isochroman.
Scheme 31: Co-catalyzed C–H alkylation of (benz)oxazoles with ethers.
Scheme 32: Cobalt-catalyzed CDC between unactivated C(sp2)–H and C(sp3)–H bonds.
Scheme 33: MnO2-catalyzed CDC of the inactive C(sp3)-H.
Scheme 34: Oxidative cross-coupling of ethers with enamides.
Scheme 35: Ni(II)-catalyzed CDC of indoles with 1,4-dioxane.
Scheme 36: Chemo- and regioselective ortho- or para-alkylation of pyridines.
Scheme 37: Asymmetric CDC of 3,6-dihydro-2H-pyrans with aldehydes.
Scheme 38: CDC of heterocyclic aromatics with ethers.
Scheme 39: Indium-catalyzed alkylation of DHPs with 1,3-dicarbonyl compounds.
Scheme 40: Rare earth-metal-catalyzed CDC reaction.
Scheme 41: Visible-light-driven CDC of cycloalkanes with benzazoles.
Scheme 42: Photoinduced alkylation of quinoline with cyclic ethers.
Scheme 43: Photocatalyzed CDC reactions between α-C(sp3)–H bonds of ethers and C(sp2)–H bonds of aromatics.
Chemical syntheses and salient features of azulene-containing homo- and copolymers
- Vijayendra S. Shetti
Beilstein J. Org. Chem. 2021, 17, 2164–2185, doi:10.3762/bjoc.17.139
- -dibromo-6-(n-dodecyl)azulene (13) with 2,5-bis(trimethylstannyl)thiophene (44) under Stille reaction conditions produced the polymer 45 in 62% yield (Scheme 10). The Mn and PDI for polymer 45 were 5100 Da and 1.4, respectively and its thermal stability was excellent (Td = 404 °C). Polymer 45 exhibited
- bis-stannylated bithiophene 60 with varying ratios of dibromoazulenes 4 and 12 under Stille reaction conditions furnished the azulene-bithiophene copolymers 61–65 in decent yields (Scheme 13B). The final composition of the 1,3- and 4,7-regioisomers of azulene in the polymer chain was determined by 1H
- )thiophene (44) under Stille reaction conditions yielded poly(2-arylazulene-alt-thiophene) 99–101 in good yields (Scheme 18B). All three polymers possessed good thermal stability and their Mn was in the range of 6900 to 12000 Da. Their absorption maxima were around 350 nm in chloroform solution and were red
Graphical Abstract
Figure 1: Chemical structure, numbering scheme, and resonance form of azulene.
Scheme 1: Synthesis of polyazulene-iodine (PAz-I2) and polyazulene-bromine (PAz-Br2) complexes.
Scheme 2: Synthesis of ‘true polyazulene’ 3 or 3’ by cationic polymerization.
Scheme 3: Synthesis of 1,3-polyazulene 5 by Yamamoto protocol.
Scheme 4: Synthesis of 4,7-dibromo-6-(n-alkyl)azulenes 12–14.
Scheme 5: Synthesis of (A) 4,7-diethynyl-6-(n-dodecyl)azulene (16) and (B) 4,7-polyazulene 17 containing an e...
Scheme 6: Synthesis of directly connected 4,7-polyazulenes 18–20.
Scheme 7: Synthesis of (A) tert-butyl N-(6-bromoazulen-2-yl)carbamate (27), (B) dimeric aminoazulene 29, and ...
Figure 2: Iminium zwitterionic resonance forms of poly[2(6)-aminoazulene] 31.
Scheme 8: Synthesis of poly{1,3-bis[2-(3-alkylthienyl)]azulene} 33–38.
Scheme 9: Synthesis of polymer ruthenium complexes 40–43.
Scheme 10: Synthesis of 4,7-polyazulenes 45 containing a thienyl linker.
Scheme 11: Synthesis of azulene-bithiophene 48 and azulene-benzothiadiazole 52 copolymers. Conditions: (a): (i...
Scheme 12: Synthesis of azulene-benzodithiophene copolymer 54 and azulene-bithiophene copolymer 56.
Scheme 13: Synthesis of (A) 5,5’-bis(trimethylstannyl)-3,3’-didodecyl-2,2’-bithiophene (60) and (B) azulene-bi...
Scheme 14: Synthesis of 1,3-bisborylated azulene 67.
Scheme 15: Synthesis of D–A-type azulene-DPP copolymers 69, 71, and 72. Conditions: (a) Pd(PPh3)4, K2CO3, Aliq...
Scheme 16: Synthesis of the key precursor TBAzDI 79.
Scheme 17: Synthesis of TBAzDI-based polymers 81 and 83. Conditions: (a) P(o-tol)3, Pd2(dba)3, PivOH, Cs2CO3, ...
Scheme 18: Synthesis of (A) 1,3-dibromo-2-arylazulene 92–98 and (B) 2-arylazulene-thiophene copolymers 99–101.
Scheme 19: Synthesis of (A) poly[2,7-(9,9-dialkylfluorenyl)-alt-(1’,3’-azulenyl)] 106–109, (B) 1,3-bis(7-bromo...
Scheme 20: Synthesis of azulene-fluorene copolymers 117–121 containing varying ratios of 1,3- and 4,7-connecte...
Scheme 21: Synthesis of (A) 2,6-dibromoazulene (125), (B) azulene-fluorene copolymer 126, and (C) azulene-fluo...
Scheme 22: Synthesis of 2-arylazulene-fluorene copolymers 131–134.
Scheme 23: Synthesis of azulene-fluorene-benzothiadiazole terpolymers 136–138.
Scheme 24: Synthesis of azulene-carbazole-benzothiadiazole-conjugated polymers 140–144.
Scheme 25: Synthesis of (A) azulene-2-yl methacrylate (146) and (B) the triazole-containing azulene methacryla...
Scheme 26: Synthesis of (A) azulene methacrylate polymer 151 and (B) triazole-containing azulene methacrylate ...
Scheme 27: Synthesis of azulene methyl methacrylate polymers 154, 155 (A and B) and azulene-sulfobetaine metha...
Progress in the total synthesis of inthomycins
- Bidyut Kumar Senapati
Beilstein J. Org. Chem. 2021, 17, 58–82, doi:10.3762/bjoc.17.7
- PdCl2(MeCN)2 produced (E,E,E)-triene 32 in 84% yield. Finally, NaBH4 reduction of 32 gave alcohol (rac)-13, in which the triene moiety is analogous to inthomycin C ((rac)-3) and oxazolomycin B (5b) (Scheme 2). After the successful application of the Stille reaction to construct the (E,E,E)-triene system
Graphical Abstract
Figure 1: The inthomycins A–C (1–3) and structurally closely related compounds.
Figure 2: Syntheses of inthomycins A–C (1–3).
Scheme 1: The first total synthesis of racemic inthomycin A (rac)-1 by Whiting.
Scheme 2: Moloney’s synthesis of the phenyl analogue of inthomycin C ((rac)-3).
Scheme 3: Moloney’s synthesis of phenyl analogues of inthomycins A (rac-1) and B (rac-2).
Scheme 4: The first total synthesis of inthomycin B (+)-2 by R. J. K. Taylor.
Scheme 5: R. J. K. Taylor’s total synthesis of racemic inthomycin A (rac)-1.
Scheme 6: The first total synthesis of inthomycin C ((+)-3) by R. J. K. Taylor.
Scheme 7: The first total synthesis of naturally occurring inthomycin C ((–)-3) by Ryu et al.
Scheme 8: Preparation of E,E-iododiene (+)-84 and Z,E- iododiene 85a.
Scheme 9: Hatakeyama’s total synthesis of inthomycin A (+)-1 and inthomycin B (+)-2.
Scheme 10: Hatakeyama’s total synthesis of inthomycin C ((–)-3).
Scheme 11: Maulide’s formal synthesis of racemic inthomycin C ((rac)-3).
Scheme 12: Hale’s synthesis of dienylstannane (+)-69 and enyne (+)-82b intermediates.
Scheme 13: Hale’s total synthesis of inthomycin C ((+)-3).
Scheme 14: Hale and Hatakeyama’s resynthesis of (3R)-inthomycin C (−)-3 Mosher esters.
Scheme 15: Reddy’s formal syntheses of inthomycin C (+)-3 and inthomycin C ((−)-3).
Scheme 16: Synthesis of the cross-metathesis precursors (rac)-118 and 121.
Scheme 17: Donohoe’s total synthesis of inthomycin C ((−)-3).
Scheme 18: Synthesis of dienylboronic ester (E,E)-128.
Scheme 19: Synthesis of the alkenyl iodides (Z)- and (E)-130.
Scheme 20: Burton’s total synthesis of inthomycin B ((+)-2).
Scheme 21: Burton’s total synthesis of inthomycin C ((−)-3).
Scheme 22: Burton’s total synthesis of inthomycin A ((+)-1).
Scheme 23: Synthesis of common intermediate (Z)-(+)-143a.
Scheme 24: Synthesis of (Z)-and (E)-selective fragments (+)-145a–c.
Scheme 25: Kim’s total synthesis of inthomycins A (+)-1 and B (+)-2.
Scheme 26: Completion of total synthesis of inthomycin C ((–)-3) by Kim.
5-Aminopyrazole as precursor in design and synthesis of fused pyrazoloazines
- Ranjana Aggarwal and
- Suresh Kumar
Beilstein J. Org. Chem. 2018, 14, 203–242, doi:10.3762/bjoc.14.15
- . Chlorination of pyrazolo[3,4-d]pyrimidine derivative 211 with phosphorus oxychloride afforded 4-chloro-1H-pyrazolo[3,4-d]pyrimidine derivative 212. The chloro and nitro groups were manipulated to introduce a 3,6-dihydropyran group at position-4 by Stille reaction which provided 4-(4-(3,6-dihydropyran-4-yl)-1H
Graphical Abstract
Figure 1: Selected examples of drugs with fused pyrazole rings.
Figure 2: Typical structures of some fused pyrazoloazines from 5-aminopyrazoles.
Scheme 1: Regiospecific synthesis of 4 and 6-trifluoromethyl-1H-pyrazolo[3,4-b]pyridines.
Scheme 2: Synthesis of pyrazolo[3,4-b]pyridine-6-carboxylates.
Scheme 3: Synthesis of 1,4,6-triaryl-1H-pyrazolo[3,4-b]pyridines with ionic liquid .
Scheme 4: Synthesis of coumarin-based isomeric tetracyclic pyrazolo[3,4-b]pyridines.
Scheme 5: Synthesis of 6-substituted pyrazolo[3,4-b]pyridines under Heck conditions.
Scheme 6: Microwave-assisted palladium-catalyzed synthesis of pyrazolo[3,4-b]pyridines.
Scheme 7: Acid-catalyzed synthesis of pyrazolo[3,4-b]pyridines via enaminones.
Scheme 8: Synthesis of pyrazolo[3,4-b]pyridines via aza-Diels–Alder reaction.
Scheme 9: Synthesis of macrocyclane fused pyrazolo[3,4-b]pyridine derivatives.
Scheme 10: Three-component synthesis of 4,7-dihydro-1H-pyrazolo[3,4-b]pyridine derivatives.
Scheme 11: Ultrasonicated synthesis of spiro[indoline-3,4'-pyrazolo[3,4-b]pyridine]-2,6'(1'H)-diones.
Scheme 12: Synthesis of spiro[indoline-3,4'-pyrazolo[3,4-b]pyridine] derivatives under conventional heating co...
Scheme 13: Nanoparticle-catalyzed synthesis of pyrazolo[3,4-b]pyridine-spiroindolinones.
Scheme 14: Microwave-assisted multicomponent synthesis of spiropyrazolo[3,4-b]pyridines.
Scheme 15: Unexpected synthesis of naphthoic acid-substituted pyrazolo[3,4-b]pyridines.
Scheme 16: Multicomponent synthesis of variously substituted pyrazolo[3,4-b]pyridine derivatives.
Scheme 17: Three-component synthesis of 4,7-dihydropyrazolo[3,4-b]pyridines and pyrazolo[3,4-b]pyridines.
Scheme 18: Synthesis of pyrazolo[3,4-b]pyridine-5-spirocycloalkanediones.
Scheme 19: Ultrasound-mediated three-component synthesis of pyrazolo[3,4-b]pyridines.
Scheme 20: Multicomponent synthesis of 4-aryl-3-methyl-1-phenyl-4,6,8,9-tetrahydropyrazolo [3,4-b]thiopyrano[4...
Scheme 21: Synthesis of 2,3-dihydrochromeno[4,3-d]pyrazolo[3,4-b]pyridine-1,6-diones.
Scheme 22: FeCl3-catalyzed synthesis of o-hydroxyphenylpyrazolo[3,4-b]pyridine derivatives.
Scheme 23: Ionic liquid-mediated synthesis of pyrazolo[3,4-b]pyridines.
Scheme 24: Microwave-assisted synthesis of pyrazolo[3,4-b]pyridines.
Scheme 25: Multicomponent synthesis of pyrazolo[3,4-b]pyridine-5-carbonitriles.
Scheme 26: Unusual domino synthesis of 4,7-dihydropyrazolo[3,4-b]pyridine-5-nitriles.
Scheme 27: Synthesis of 4,5,6,7-tetrahydro-4H-pyrazolo[3,4-b]pyridines under conventional heating and ultrasou...
Scheme 28: L-Proline-catalyzed synthesis of of pyrazolo[3,4-b]pyridine.
Scheme 29: Microwave-assisted synthesis of 5-aminoarylpyrazolo[3,4-b]pyridines.
Scheme 30: Microwave-assisted multi-component synthesis of pyrazolo[3,4-e]indolizines.
Scheme 31: Synthesis of fluoropropynyl and fluoroalkyl substituted pyrazolo[1,5-a]pyrimidine.
Scheme 32: Acid-catalyzed synthesis of pyrazolo[1,5-a]pyrimidine derivatives.
Scheme 33: Chemoselective and regiospecific synthesis of 2-(3-methylpyrazol-1’-yl)-5-methylpyrazolo[1,5-a]pyri...
Scheme 34: Regioselective synthesis of 7-trifluoromethylpyrazolo[1,5-a]pyrimidines.
Scheme 35: Microwave-assisted synthesis of 7-trifluoromethylpyrazolo[1,5-a]pyrimidine carboxylates.
Scheme 36: Microwave and ultrasound-assisted synthesis of 7-trifluoromethylpyrazolo[1,5-a]pyrimidines.
Scheme 37: Base-catalyzed unprecedented synthesis of pyrazolo[1,5-a]pyrimidines via C–C bond cleavage.
Scheme 38: Synthesis of aminobenzothiazole/piperazine linked pyrazolo[1,5-a]pyrimidines.
Scheme 39: Synthesis of aminoalkylpyrazolo[1,5-a]pyrimidine-7-amines.
Scheme 40: Synthesis of pyrazolo[1,5-a]pyrimidines from condensation of 5-aminopyrazole 126 and ethyl acetoace...
Scheme 41: Synthesis of 7-aminopyrazolo[1,5-a]pyrimidines.
Scheme 42: Unexpected synthesis of 7-aminopyrazolo[1,5-a]pyrimidines under solvent free and solvent-mediated c...
Scheme 43: Synthesis of N-(4-aminophenyl)-7-aryloxypyrazolo[1,5-a]pyrimidin-5-amines.
Scheme 44: Base-catalyzed synthesis of 5,7-diarylpyrazolo[1,5-a]pyrimidines.
Scheme 45: Synthesis of 6,7-dihydropyrazolo[1,5-a]pyrimidines in PEG-400.
Scheme 46: Synthesis of 7-heteroarylpyrazolo[1,5-a]pyrimidine-3-carboxamides.
Scheme 47: Synthesis of 7-heteroarylpyrazolo[1,5-a]pyrimidine derivatives under conventional heating and micro...
Scheme 48: Synthesis of N-aroylpyrazolo[1,5-a]pyrimidine-5-amines.
Scheme 49: Regioselective synthesis of ethyl pyrazolo[1,5-a]pyrimidine-7-carboxylate.
Scheme 50: Sodium methoxide-catalyzed synthesis of 3-cyano-6,7-diarylpyrazolo[1,5-a]pyrimidines.
Scheme 51: Synthesis of various pyrazolo[3,4-d]pyrimidine derivatives.
Scheme 52: Synthesis of hydrazinopyrazolo[3,4-d]pyrimidine derivatives.
Scheme 53: Synthesis of N-arylidinepyrazolo[3,4-d]pyrimidin-5-amines.
Scheme 54: Synthesis of pyrazolo[3,4-d]pyrimidinyl-4-amines.
Scheme 55: Iodine-catalyzed synthesis of pyrazolo[3,4-d]pyrimidinones.
Scheme 56: Synthesis of ethyl 6-amino-2H-pyrazolo[3,4-d]pyrimidine-4-carboxylate.
Scheme 57: Synthesis of 4-substituted-(3,6-dihydropyran-4-yl)-1H-pyrazolo[3,4-d]pyrimidines.
Scheme 58: Synthesis of 1-(2,4-dichlorophenyl)pyrazolo[3,4-d]pyrimidin-4-yl carboxamides.
Scheme 59: Synthesis of 5-(1,3,4-thidiazol-2-yl)pyrazolo[3,4-d]pyrimidine.
Scheme 60: One pot POCl3-catalyzed synthesis of 1-arylpyrazolo[3,4-d]pyrimidin-4-ones.
Scheme 61: Synthesis of 4-amino-N1,C3-dialkylpyrazolo[3,4-d]pyrimidines under Suzuki conditions.
Scheme 62: Microwave-assisted synthesis of pyrazolo[3,4-b]pyrazines.
Scheme 63: Synthesis and derivatization of pyrazolo[3,4-b]pyrazine-5-carbonitriles.
Scheme 64: Synthesis of 2-thioxo-pyrazolo[1,5-a][1,3,5]triazin-4-ones.
Scheme 65: Synthesis of 2,3-dihydropyrazolo[1,5-a][1,3,5]triazin-4(1H)-one.
Scheme 66: Synthesis of pyrazolo[1,5-a][1,3,5]triazine-8-carboxylic acid ethyl ester.
Scheme 67: Microwave-assisted synthesis of 4,7-dihetarylpyrazolo[1,5-a][1,3,5]triazines.
Scheme 68: Alternative synthetic route to 4,7-diheteroarylpyrazolo[1,5-a][1,3,5]triazines.
Scheme 69: Synthesis of 4-aryl-2-ethylthio-7-methylpyrazolo[1,5-a][1,3,5]triazines.
Scheme 70: Microwave-assisted synthesis of 4-aminopyrazolo[1,5-a][1,3,5]triazine.
Scheme 71: Synthesis of pyrazolo[3,4-d][1,2,3]triazines from pyrazol-5-yl diazonium salts.
Scheme 72: Synthesis of 2,5-dihydropyrazolo[3,4-e][1,2,4]triazines.
Scheme 73: Synthesis of pyrazolo[5,1-c][1,2,4]triazines via diazopyrazolylenaminones.
Scheme 74: Synthesis of pyrazolo[5,1-c][1,2,4]triazines in presence of sodium acetate.
Scheme 75: Synthesis of various 7-diazopyrazolo[5,1-c][1,2,4]triazine derivatives.
Scheme 76: One pot synthesis of pyrazolo[5,1-c][1,2,4]triazines.
Scheme 77: Synthesis of 4-amino-3,7,8-trinitropyrazolo-[5,1-c][1,2,4]triazines.
Scheme 78: Synthesis of tricyclic pyrazolo[5,1-c][1,2,4]triazines by azocoupling reaction.
Total synthesis of elansolids B1 and B2
- Liang-Liang Wang and
- Andreas Kirschning
Beilstein J. Org. Chem. 2017, 13, 1280–1287, doi:10.3762/bjoc.13.124
- an optimized C–C cross-coupling sequence with a Suzuki cross-coupling reaction as key step. Keywords: antibiotics; polyenes; polyketides; Stille reaction; Suzuki reaction; total synthesis; Introduction The elansolids are metabolites from the gliding bacterium Chitinophaga sancti (formerly
Graphical Abstract
Figure 1: Elansolids A1/A2, B1, B2 and A3 (1–4).
Scheme 1: IMDA to generate the tetrahydroindane unit of the elansolids by oxidation of benzyl ether 8 as prec...
Scheme 2: Stille cross-coupling reaction and formation of eastern fragment 13.
Scheme 3: Total synthesis of elansolids B1 (2) and B2 (3).
Total syntheses of the archazolids: an emerging class of novel anticancer drugs
- Stephan Scheeff and
- Dirk Menche
Beilstein J. Org. Chem. 2017, 13, 1085–1098, doi:10.3762/bjoc.13.108
- could successfully couple the three main fragments 39, 40 and 6 by first a Stille reaction, followed by a Kita esterification. Notably, this esterification was critical to avoid unfavorable isomerizations. For closing of the macrolide core they planned a challenging Hoye relay ring closing metathesis
Graphical Abstract
Scheme 1: Molecular structures of the archazolids.
Scheme 2: Retrosynthetic analysis of archazolid A by the Menche group.
Scheme 3: Synthesis of north-eastern fragment 5 through a Paterson anti-aldol addition and multiple Still–Gen...
Scheme 4: Synthesis of 4 through an Abiko–Masamune anti-aldol addition.
Scheme 5: Thiazol construction and synthesis of the southern fragment 6.
Scheme 6: Completion of the total synthesis of archazolid A.
Scheme 7: Synthesis of archazolid B (2) by a ring closing Heck reaction of 38.
Scheme 8: Retrosynthetic analysis of archazolid B by the Trauner group.
Scheme 9: Synthesis of acid 40 from Roche ester 41 involving a highly efficient Trost–Alder ene reaction.
Scheme 10: Synthesis of precursor 39 for the projected relay RCM reaction.
Scheme 11: Final steps of Trauner’s total synthesis of archazolid B.
Scheme 12: Overview of the different retrosynthetic approaches for the synthesis of dihydroarchazolid B (3) re...
Scheme 13: Fragment synthesis of 69 towards the total synthesis of 3.
Scheme 14: Organometallic addition of the side chain to access free alcohol 75.
Molecular-level architectural design using benzothiadiazole-based polymers for photovoltaic applications
- Vinila N. Viswanathan,
- Arun D. Rao,
- Upendra K. Pandey,
- Arul Varman Kesavan and
- Praveen C. Ramamurthy
Beilstein J. Org. Chem. 2017, 13, 863–873, doi:10.3762/bjoc.13.87
- compound was then coupled with trimethyl(thiophene-2-yl)stannane through a Stille reaction using tris(dibenzylideneacetone)dipalladium(0) and tri-o-tolylphosphine as the catalyst system. The dithiophenylated product 3 was washed several times with methanol to remove the palladium catalyst and other
Graphical Abstract
Scheme 1: Synthetic route towards monomers M1, M2 and M3.
Scheme 2: Synthesis of polymers P1, P2, and P3.
Figure 1: Isodensity surface plots of frontier molecular orbitals and optimized molecular geometries of P1, P2...
Figure 2: Theoretical absorption spectra of the polymers P1–P3 calculated using TDDFT.
Figure 3: Electrochemical spectra of polymers P1–P3.
Figure 4: Normalized absorption spectra of the polymers in solution, film and annealed film (130 °C) forms.
Figure 5: Photoluminescence spectra of polymers P1–P3 and polymer:PC70BM blends.
Figure 6: Bulk heterojunction solar cells device architecture, illustrating favorable conditions for absorpti...
Figure 7: J–V Spectra in chlorobenzene (CB) for which the ratio of polymer:PC70BM was optimized as follows: P1...
Figure 8: External quantum efficiency spectra of optimized devices fabricated with polymers P1, P2 and P3 and...
Effects of solvent additive on “s-shaped” curves in solution-processed small molecule solar cells
- John A. Love,
- Shu-Hua Chou,
- Ye Huang,
- Guilllermo C. Bazan and
- Thuc-Quyen Nguyen
Beilstein J. Org. Chem. 2016, 12, 2543–2555, doi:10.3762/bjoc.12.249
- 3 was obtained through lithium–halogen exchange with n-BuLi followed by addition of trimethyltin chloride. Segments 2 and 3 were cross-coupled using a microwave-assisted Stille reaction to afford the target p-SIDT(FBTThCA8)2. The thermal transitions of p-SIDT(FBTThCA8)2 were evaluated by
Graphical Abstract
Figure 1: a) Molecular structures and b) energy levels of p-SIDT(FBTTh2)2 and p-SIDT(FBTThCA8)2 highlighting ...
Scheme 1: Synthetic route towards p-SIDT(FBTThCA8)2. (i) Sn2Me6, Pd(PPh3)4, toluene, 85 °C; (ii) 4,7-dibromo-...
Figure 2: a) Solid-state absorption profiles of neat p-SIDT(FBTThCA8)2 (dashed line) and p-SIDT(FBTThCA8)2:PC...
Figure 3: Light intensity dependence of photocurrent as a function of the effective voltage, V0 − V, for devi...
Figure 4: Current voltage curves for devices cast from pure chlorobenzene (yellow) and with 1.5% DIO (blue) w...
Figure 5: Dynamic secondary ion mass spectrometry (DSIMS) profile showing scaled nitrogen (solid) and deuteri...
Figure 6: a) A schematic diagram of inverted architecture and b) J–V curves of device cast with no DIO in the...
Efficient synthesis of π-conjugated molecules incorporating fluorinated phenylene units through palladium-catalyzed iterative C(sp2)–H bond arylations
- Fatiha Abdelmalek,
- Fazia Derridj,
- Safia Djebbar,
- Jean-François Soulé and
- Henri Doucet
Beilstein J. Org. Chem. 2015, 11, 2012–2020, doi:10.3762/bjoc.11.218
- -coupling reactions are one of the most powerful technologies for the efficient synthesis of π-conjugated oligomers. As example, a π-conjugated thiophene triad incorporating a difluorinated phenylene unit has been previously synthesized in 60% yield using the Stille reaction of trimethyl(thiophen-2-yl
Graphical Abstract
Figure 1: Different pathways for the synthesis of π-conjugated molecules incorporating fluorinated phenylene ...
Scheme 1: Pd-catalyzed desulfitative direct arylations of heteroarenes using 2,3,4-trifluorobenzenesulfonyl c...
Scheme 2: Pd-catalyzed second arylation of 1 and 2. i) PdCl(C3H5)(dppb) (2 mol %), KOAc (2 equiv), DMA, 150 °...
Scheme 3: Pd-catalyzed direct regioselective arylation of 1-methyl-2-(2,3,4-trifluorophenyl)pyrrole (4). i) P...
Scheme 4: Pd-catalyzed direct regioselective arylation of 3-(2,3,4-trifluorophenyl)thiophenes. i) PdCl(C3H5)(...
Scheme 5: Pd-catalyzed desulfitative direct arylations of heteroarenes using difluorobenzenesulfonyl chloride...
Scheme 6: Pd-catalyzed second direct regioselective arylation of difluorophenylheteroarenes 19-23. i) PdCl(C3H...
Scheme 7: Pd-catalyzed iterative direct arylations of heteroarenes–fluorobenzene triads and tetrad. i) PdCl2(...
Scheme 8: Reactivity of pentafluorobenzenesulfonyl chloride in Pd-catalyzed direct desulfitative arylation of...
Synthesis of diverse indole libraries on polystyrene resin – Scope and limitations of an organometallic reaction on solid supports
- Kerstin Knepper,
- Sylvia Vanderheiden and
- Stefan Bräse
Beilstein J. Org. Chem. 2012, 8, 1191–1199, doi:10.3762/bjoc.8.132
- 25% aqueous solution of ammonium acetate are added, the resin is filtered off, washed according to the general washing procedure, and dried in high vacuum. The loading of the resulting resin was calculated as if complete conversion had taken place. GP 5 - Stille reaction: Under an argon atmosphere
- indole 3{h,d} and methyl 3-amino-4-chlorobenzoate (aniline): Isolated yields. Diverse synthesis of indoles using Bartoli reactions. aSee [24]. Stille reaction on solid supports. Suzuki reaction on solid supports. Sonogashira–Hagihara reaction on solid supports. Cleavage of indoles from solid supports
Graphical Abstract
Scheme 1: Diverse synthesis of indoles using Bartoli reactions. aSee [24].
Figure 1: Nitroarenes on solid supports. In red: Nitroarenes failed to give indoles. aResin has been reported...
Figure 2: Temperature optimization with Grignard reagent 2{b}.
Figure 3: Temperature optimization with Grignard reagent 2{a}. Isolated yield.
Figure 4: Optimization studies of ester 1{h} with a Grignard reagent 2{d} to give indole 3{h,d} and methyl 3-...
Scheme 2: Stille reaction on solid supports.
Scheme 3: Suzuki reaction on solid supports.
Scheme 4: Sonogashira–Hagihara reaction on solid supports.
Syntheses and applications of furanyl-functionalised 2,2’:6’,2’’-terpyridines
- Jérôme Husson and
- Michael Knorr
Beilstein J. Org. Chem. 2012, 8, 379–389, doi:10.3762/bjoc.8.41
- literature example for this purpose uses the Stille reaction [33]. This C–C coupling, which involves the reaction between a halogenated or equivalent starting material and an organotin compound, was used to prepare 12 from 4′-(trifluoromethanesulfonyl)-2,2′′:6′,2′′-terpyridine (34) [34] and 2
Graphical Abstract
Figure 1: Structure and atomic numbering of 2,2’:6’,2’’-terpyridines.
Scheme 1: Synthesis of furanyl-substituted terpyridines 12–14 by using Kröhnke’s method.
Scheme 2: Synthesis of terpyridines under solvent-free conditions.
Scheme 3: Preparation of 4,4′,4′′-trisubstituted terpyridine containing carboxylate moieties.
Scheme 4: Synthetic pathway for the preparation of a furanyl-functionalised quinquepyridine.
Scheme 5: Utilization of an iminium salt in the preparation of a furanyl-substituted tpy.
Figure 2: Chemical structure of U- and S-shaped isomers.
Scheme 6: Preparation of an asymmetric furanyl-substituted terpyridine.
Scheme 7: Synthesis of tpy by Stille cross-coupling reaction.
Scheme 8: Oxidation of the furan ring of furanyl-substituted terpyridines.
Scheme 9: Direct oxidation of a furan ring attached on Ru(II) tpy complexes.
Figure 3: Example of polyoxometalate frameworks functionalised with tpy ligands and tpy-complex (reprinted wi...
Scheme 10: Synthetic pathway to europium(III) and samarium(III) chelates 56 and 57.
Scheme 11: Synthetic pathway to prepare thiocyanato-functionalised tpys as potential biomolecule-labelling age...
Scheme 12: Synthetic sequence envisioned for biomolecules labelling by click-chemistry.
Figure 4: Structure of pyrrolyl (66), thienyl (67) and bithienyl (68)-substituted complexes analogous to comp...
