Photoredox catalysis harvesting multiple photon or electrochemical energies

• Mattia Lepori,
• Simon Schmid and
• Joshua P. Barham

Beilstein J. Org. Chem. 2023, 19, 1055–1145, doi:10.3762/bjoc.19.81

Heteroleptic metallosupramolecular aggregates/complexation for supramolecular catalysis

• Prodip Howlader and
• Michael Schmittel

Beilstein J. Org. Chem. 2022, 18, 597–630, doi:10.3762/bjoc.18.62

• hydride species 49 that is well known for hydroformylation reactions [77]. Incorporation of the monoligated catalyst into the confined cavity of the capsule showed very good catalytic activity towards the hydroformylation of styrene (50, Figure 11) with a high stereoselectivity (65% ee) at 32% conversion

A comprehensive review of flow chemistry techniques tailored to the flavours and fragrances industries

• Guido Gambacorta,
• James S. Sharley and
• Ian R. Baxendale

Beilstein J. Org. Chem. 2021, 17, 1181–1312, doi:10.3762/bjoc.17.90

N-tert-Butanesulfinyl imines in the asymmetric synthesis of nitrogen-containing heterocycles

• Joseane A. Mendes,
• Paulo R. R. Costa,
• Miguel Yus,
• Francisco Foubelo and
• Camilla D. Buarque

Beilstein J. Org. Chem. 2021, 17, 1096–1140, doi:10.3762/bjoc.17.86

A systematic review on silica-, carbon-, and magnetic materials-supported copper species as efficient heterogeneous nanocatalysts in “click” reactions

• Pezhman Shiri and
• Jasem Aboonajmi

Beilstein J. Org. Chem. 2020, 16, 551–586, doi:10.3762/bjoc.16.52

• delivery [93], and cancer detection [94]. In this regard, various functionalized MNPs were employed in diverse organic reactions, including Suzuki–Miyaura reactions, Sonogashira reactions, Ullmann coupling, hydrogenation reactions, oxidation reactions, hydroformylation reactions, and “click” reactions [89

KOt-Bu-promoted selective ring-opening N-alkylation of 2-oxazolines to access 2-aminoethyl acetates and N-substituted thiazolidinones

• Qiao Lin,
• Shiling Zhang and
• Bin Li

Beilstein J. Org. Chem. 2020, 16, 492–501, doi:10.3762/bjoc.16.44

• TMSN3 as the azide source [10] (Scheme 1a). Coates described a Co2(CO)8-catalyzed ring-opening hydroformylation of oxazolines for the synthesis of β-amidoaldehydes [11] (Scheme 1a). However, the ring-opening N-alkylation of 2-oxazolines to produce 2-aminoethyl acetate derivatives under basic conditions

Organometallic vs organic photoredox catalysts for photocuring reactions in the visible region

• Aude-Héloise Bonardi,
• Frédéric Dumur,
• Guillaume Noirbent,
• Jacques Lalevée and
• Didier Gigmes

Beilstein J. Org. Chem. 2018, 14, 3025–3046, doi:10.3762/bjoc.14.282

• regioselective hydroformylation of aromatic olefins [84]. Interestingly, if transition metals can initiate an ionic hydroformylation reaction of aryl olefins, a free radical pathway could be promoted by use of diethoxyacetic acid and 4CzIPN, inducing the in situ generation of an equivalent of a formyl radical

Automating multistep flow synthesis: approach and challenges in integrating chemistry, machines and logic

• Chinmay A. Shukla and
• Amol A. Kulkarni

Beilstein J. Org. Chem. 2017, 13, 960–987, doi:10.3762/bjoc.13.97

Solution-phase automated synthesis of an α-amino aldehyde as a versatile intermediate

• Hisashi Masui,
• Sae Yosugi,
• Shinichiro Fuse and
• Takashi Takahashi

Beilstein J. Org. Chem. 2017, 13, 106–110, doi:10.3762/bjoc.13.13

• serine, and the subsequent reduction of carboxylic acid derivatives such as ester [20][21][22][23][24][25][26][27], thioester [28], or Weinreb amide [29][30] to the aldehyde. In addition, Burke and co-workers reported an asymmetric hydroformylation of 2,2-dimethyl-2,3-dihydrooxazole for the synthesis of

Organometallic chemistry

• Bernd F. Straub,
• Rolf Gleiter,
• Claudia Meier and
• Lutz H. Gade

Beilstein J. Org. Chem. 2016, 12, 2216–2221, doi:10.3762/bjoc.12.213

• for olefin metathesis catalysis [86][87][90][91][98][99][100][108][132][138][147], the characterization of copper–carbene complexes as intermediates in the cyclopropanation of alkenes [102][106][113][119][120], as well as detailed studies into the mechanism of the hydroformylation of alkenes. An

Scope and limitations of a DMF bio-alternative within Sonogashira cross-coupling and Cacchi-type annulation

• Kirsty L. Wilson,
• Alan R. Kennedy,
• Jane Murray,
• Ben Greatrex,
• Craig Jamieson and
• Allan J. B. Watson

Beilstein J. Org. Chem. 2016, 12, 2005–2011, doi:10.3762/bjoc.12.187

• ][35], Mizoroki–Heck [36][37], Sonogashira [38], Stille [39], Hiyama reactions [40], and hydroformylation reactions [41]. In the current study, we present the use of Cyrene as an alternative solvent (direct DMF replacement) for the Sonogashira reaction, as well as related Cacchi-type annulations [42

Recent advances in metathesis-derived polymers containing transition metals in the side chain

• Ileana Dragutan,
• Valerian Dragutan,
• Bogdan C. Simionescu,
• Albert Demonceau and
• Helmut Fischer

Beilstein J. Org. Chem. 2015, 11, 2747–2762, doi:10.3762/bjoc.11.296

• copolymer 39 (Scheme 16). Remarkably, in water, this Rh-containing block copolymer readily generated micelles and could be thus successfully employed as a Rh-immobilized catalyst for the hydroformylation of 1-octene. Very recently, Matyjaszewski, Tang and coworkers [62] reported the first synthesis of

Hydrogenation of unactivated enamines to tertiary amines: rhodium complexes of fluorinated phosphines give marked improvements in catalytic activity

• Sergey Tin,
• Tamara Fanjul and
• Matthew L. Clarke

Beilstein J. Org. Chem. 2015, 11, 622–627, doi:10.3762/bjoc.11.70

• to be addressed with new catalysts. In a recent study on hydroaminomethylation, i.e., domino hydroformylation–enamine formation–enamine hydrogenation, we noted that the enamine hydrogenation was the slowest reaction in the process, and use of an electron-deficient phosphine sped up the reduction step

• regioselectivity in enantioselective hydroformylation of alkyl- and arylalkenes [23][24], we reconsidered this cyclisation reaction using the new catalyst (Scheme 2). We were pleased to find that the selectivity is increased to 78%. Since the desired product is achiral, there is no need to use enantiopure BOBPHOS

Novel stereocontrolled syntheses of tashiromine and epitashiromine

• Loránd Kiss,
• Enikő Forró and
• Ferenc Fülöp

Beilstein J. Org. Chem. 2015, 11, 596–603, doi:10.3762/bjoc.11.66

• the indolizidine framework; access to tashiromine in racemic form can be achieved through the alkylation of succinimide, followed by ring closure via acyliminium intermediates [23][24], the reduction of cyclized pyridinium salts [25], iminium cascade cyclization [26], alkyne-mediated hydroformylation

Cyclodextrin-grafted polymers functionalized with phosphanes: a new tool for aqueous organometallic catalysis

• Jonathan Potier,
• Stéphane Menuel,
• David Mathiron,
• Véronique Bonnet,
• Frédéric Hapiot and
• Eric Monflier

Beilstein J. Org. Chem. 2014, 10, 2642–2648, doi:10.3762/bjoc.10.276

• used as additives in Rh-catalyzed hydroformylation of 1-hexadecene. The combined supramolecular and coordinating properties of these polymers allowed increasing the catalytic activity of the reaction without affecting the selectivities. Keywords: biphasic catalysis; cyclodextrin; hydroformylation

• interface to favour the substrate conversion. Herein, we detailed the synthesis and characterisation of this polymer and its catalytic behaviour in Rh-catalyzed hydroformylation of 1-hexadecene. Results and Discussion A wide range of CD-based polymers have already been described in the literature [13][14

• 3a that did not contain any phosphane has also been synthesized (Mn = 11400 g·mol−1, Đ = 1.23). The catalytic performances of polymers 3a, 3b and 3c have been evaluated in a Rh-catalyzed hydroformylation of 1-hexadecene at 80 °C under 50 bar CO/H2 in a 1/1 stoichiometric ratio. The results were

Phosphinocyclodextrins as confining units for catalytic metal centres. Applications to carbon–carbon bond forming reactions

• Matthieu Jouffroy,
• Rafael Gramage-Doria,
• David Sémeril,
• Dominique Armspach,
• Dominique Matt,
• Werner Oberhauser and
• Loïc Toupet

Beilstein J. Org. Chem. 2014, 10, 2388–2405, doi:10.3762/bjoc.10.249

• -catalysed Mizoroki–Heck coupling reactions between aryl bromides and styrene on one hand, and the rhodium-catalysed asymmetric hydroformylation of styrene on the other hand. The inability of both chiral ligands to form standard bis(phosphine) complexes under catalytic conditions was established by high

• -pressure NMR studies and shown to have a deep impact on the two carbon–carbon bond forming reactions both in terms of activity and selectivity. For example, when used as ligands in the rhodium-catalysed hydroformylation of styrene, they lead to both high isoselectivity and high enantioselectivity. In the

• study dealing with the Mizoroki–Heck reactions, comparative tests were carried out with WIDEPHOS, a diphosphine analogue of HUGPHOS-2. Keywords: asymmetric hydroformylation; cyclodextrin; Heck reaction; homogeneous catalysis; palladium; phosphine; rhodium; Introduction Since the studies of Fu

An overview of the synthetic routes to the best selling drugs containing 6-membered heterocycles

• Marcus Baumann and
• Ian R. Baxendale

Beilstein J. Org. Chem. 2013, 9, 2265–2319, doi:10.3762/bjoc.9.265

Camera-enabled techniques for organic synthesis

• Steven V. Ley,
• Richard J. Ingham,
• Matthew O’Brien and
• Duncan L. Browne

Beilstein J. Org. Chem. 2013, 9, 1051–1072, doi:10.3762/bjoc.9.118

• hydroformylation reaction. Without the extraction step the hydroformylation step was unsuccessful; experiments suggested that this was due to the amine base or its salts. In the reactor configuration used in this work (Figure 32), the output from the ethylene-Heck reaction is combined with an aqueous stream to

Impact of cyclodextrins on the behavior of amphiphilic ligands in aqueous organometallic catalysis

• Hervé Bricout,
• Estelle Léonard,
• Christophe Len,
• David Landy,
• Frédéric Hapiot and
• Eric Monflier

Beilstein J. Org. Chem. 2012, 8, 1479–1484, doi:10.3762/bjoc.8.167

• substrates constitutes a real challenge not completely solved so far. Recently, we showed that an association of cyclodextrins (CDs) and amphiphilic phosphanes could significantly improve the catalytic performances in an aqueous rhodium-catalyzed hydroformylation of higher olefins [6]. Herein we clearly

Efficient and selective chemical transformations under flow conditions: The combination of supported catalysts and supercritical fluids

• M. Isabel Burguete,
• Eduardo García-Verdugo and
• Santiago V. Luis

Beilstein J. Org. Chem. 2011, 7, 1347–1359, doi:10.3762/bjoc.7.159

• experiments was operated to afford a stable system for five consecutive runs. For this approach, the CO2 phase was never depressurized and quantitative yields and excellent enantioselectivities (98.4% ee on average) were achieved (9 cycles, TOF > 200 h−1). 2. Hydroformylation processes Hydroformylation is

• Poliakoff and van Leeuwen [57]. A diphosphine ligand immobilized on silica was prepared by a sol–gel approach from N-[3-(tri-methoxysilyl)-n-propyl]-4,5-bis(diphenylphosphino)phenoxazine (Scheme 4). One remarkable result was that the hydroformylation rate, under flow conditions with scCO2 as the carrier

• in ionic liquids (ILs) The immobilization of a Rh hydroformylation catalyst in [BMIM][PF6] has been reported by Cole-Hamilton to produce a significant decrease in the aldehyde selectivity, relative to toluene, while retaining the conversion and the l/b selectivity [60][61]. Changing to a scCO2–IL

Ring opening metathesis polymerization-derived block copolymers bearing chelating ligands: synthesis, metal immobilization and use in hydroformylation under micellar conditions

• Gajanan M. Pawar,
• Jochen Weckesser,
• Siegfried Blechert and
• Michael R. Buchmeiser

Beilstein J. Org. Chem. 2010, 6, No. 28, doi:10.3762/bjoc.6.28

• copolymer poly(M1-b-M2)-Rh containing 18 mg of Rh(I)/g of block copolymer with a cmc of 2.2 × 10−6 mol L−1. The Rh-loaded polymer was used for the hydroformylation of 1-octene under micellar conditions. The data obtained were compared to those obtained with a monomeric analogue, i.e. CH3CON(Py)2RhCl(COD

• N,N-dipyrid-2-ylacetamide and their use in hydroformylation reactions [9]. Here, we report on the immobilization of a Rh-N,N-dipyrid-2-ylacetamide-based catalyst on a soluble, amphiphilic, ring-opening metathesis polymerization- (ROMP) derived block copolymer and its use in hydroformylation [10

• measurements. A value of 2.2 × 10−6 mol L−1 was found, indicating that the loading with Rh(I) hardly changes the cmc value (Figure S4, Supporting Information File 1). Hydroformylation under micellar conditions Generally, micellar catalysis [3][5][24][25][26][27][28] and in particular micellar set-ups, where

Synthesis of (–)-Indolizidine 167B based on domino hydroformylation/cyclization reactions

• Giuditta Guazzelli,
• Raffaello Lazzaroni and
• Roberta Settambolo

Beilstein J. Org. Chem. 2008, 4, No. 2, doi:10.1186/1860-5397-4-2

• Chimica e Chimica Industriale, Università di Pisa, Via Risorgimento 35, 56126 Pisa, Italy 10.1186/1860-5397-4-2 Abstract The synthesis of (–)-Indolizidine 167B has been achieved from optically active (R)-3-(pyrrol-1-yl)hex-1-ene. The key step is a highly regioselective hydroformylation reaction and a one

• Indolizidine 167B depicted here the construction of the bicyclic core still occurs via a pyrrolylbutanal; unlike the previous case, the aldehyde comes from rhodium-catalyzed hydroformylation of optically active (R)-3-(pyrrol-1-yl)hex-1-ene (1) (Scheme 1). The formed linear aldehyde 2a (Scheme 2), bearing an n

• reduction gives the target compound (ee 92%) (Scheme 1). The rhodium-catalyzed hydroformylation of olefins is an important industrial tool for the production of aldehydes [10][11]. During the last few years, the oxo process has been employed also in the synthesis of fine chemicals especially integrated in

Mixtures of monodentate P-ligands as a means to control the diastereoselectivity in Rh-catalyzed hydrogenation of chiral alkenes

• Manfred T. Reetz and
• Hongchao Guo

Beilstein J. Org. Chem. 2005, 1, No. 3, doi:10.1186/1860-5397-1-3

• ligand composed of building blocks derived from the particular ligands La and Lb. We have recently extended this combinatorial principle beyond enantioselectivity[19][20][21][22][23][24][25][26] to include regioselectivity,[28] specifically in the hydroformylation of methacrylic acid tert-butyl ester. By