Advancements in hydrochlorination of alkenes

• Daniel S. Müller

Beilstein J. Org. Chem. 2024, 20, 787–814, doi:10.3762/bjoc.20.72

• hydrochlorination of 1-octene (63) required a combination of alumina and oxalyl chloride (Table 5, entry 3). It should be noted that this reaction needs to be carried out under a well-ventilated hood due to the evolution of toxic carbon monoxide. Kropp and co-workers observed that the remaining 2% of the alkene was

• , enabling the hydrochlorination of 1-octene (63) in the presence of 15 equivalents of hydrochloric acid (Scheme 19). The reaction necessitates heating to 115 °C for 2 days to achieve 90% conversion and a 75% isolated yield of 41. Conversely, the reaction with styrene (3) is complete within one hour

• , the conditions for the hydrochlorination of alkenes had to be adapted for each alkene. Whereas reactive alkenes gave the corresponding chlorides within several hours at room temperature, terminal alkenes required harsher reaction conditions. 1-Octene (63) gave under these conditions a mixture of the

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

• hydroarylation of tert-butyl vinylcarbamate and unactivated alkenes like 1-octene and 3-buten-1-ol although the vinyl carbamate substrate (Epred = −2.2 V vs SCE) is significantly easier to reduce than most aryl chlorides. This selectivity, especially considering the need for an excess of the vinyl carbamate

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

The preparation and properties of 1,1-difluorocyclopropane derivatives

• Kymbat S. Adekenova,
• Peter B. Wyatt and
• Sergazy M. Adekenov

Beilstein J. Org. Chem. 2021, 17, 245–272, doi:10.3762/bjoc.17.25

Pauson–Khand reaction of fluorinated compounds

• Jorge Escorihuela,
• Daniel M. Sedgwick,
• Alberto Llobat,
• Mercedes Medio-Simón,
• Pablo Barrio and
• Santos Fustero

Beilstein J. Org. Chem. 2020, 16, 1662–1682, doi:10.3762/bjoc.16.138

• cyclohexene, maleic anhydride, ethylene carbonate, and 1-octene, the desired products were not formed under the reaction conditions. In the same year, Helaja and co-workers examined the electronic effects of the alkyne substituent on the regioselectivity of the microwave-assisted PKR with norbornene [80]. The

Vicinal difunctionalization of alkenes by four-component radical cascade reaction of xanthogenates, alkenes, CO, and sulfonyl oxime ethers

• Shuhei Sumino,
• Takahide Fukuyama,
• Mika Sasano,
• Ilhyong Ryu,
• Antoine Jacquet,
• Frédéric Robert and
• Yannick Landais

Beilstein J. Org. Chem. 2019, 15, 1822–1828, doi:10.3762/bjoc.15.176

• on the synthesis of functionalized α-keto oximes through such a one-pot, four-component procedure. Results and Discussion We first investigated the reaction of xanthate 1a [29], 1-octene (2a), CO, and sulfonyl oxime ether 3a as a model reaction. When the mixture of 1a, 2a (5 equiv), and 3a (1.2 equiv

• mechanism. Concept: Alkene difuctionalization by four-component radical reaction using xanthates, alkenes, CO and sulfonyl oxime ethers. Four-component coupling reaction of ethyl 2-((ethoxycarbonothioyl)thio)acetate (1a), 1-octene (2a), CO, and sulfonyl oxime ether 3a under radical conditionsa. Supporting

Catalysis of linear alkene metathesis by Grubbs-type ruthenium alkylidene complexes containing hemilabile α,α-diphenyl-(monosubstituted-pyridin-2-yl)methanolato ligands

• Tegene T. Tole,
• Johan H. L. Jordaan and
• Hermanus C. M. Vosloo

Beilstein J. Org. Chem. 2019, 15, 194–209, doi:10.3762/bjoc.15.19

• -methoxypyridin-2-yl)methanolato] were synthesized and tested for their activity, stability and selectivity in the 1-octene metathesis reaction. Overall the precatalysts showed good activity and high stability for the metathesis of 1-octene at temperatures above 80 °C and up to 110 °C. Selectivities towards the

• precatalysts can be attributed to electronic and steric effects associated with the adjacent bulky phenyl groups. Keywords: Grubbs-type precatalyst; hemilabile; 1-octene metathesis; pyridinyl-alcoholato ligand; Introduction The alkene metathesis reaction is now well established as a powerful synthetic tool

• Grubbs 2-type (5) metal carbenes with pyridinyl alcoholato ligands for the 1-octene metathesis reaction (Figure 3) [10][11][12][13][14]. The incorporation of pyridinyl-alcoholato ligands in the Grubbs-type precatalysts has shown an increase in the thermal stability, activity and lifetime of the

Ruthenium-based olefin metathesis catalysts with monodentate unsymmetrical NHC ligands

• Veronica Paradiso,
• Chiara Costabile and
• Fabia Grisi

Beilstein J. Org. Chem. 2018, 14, 3122–3149, doi:10.3762/bjoc.14.292

• saturated NHC ligand containing a N-substituted cyclododecyl side chain was first evaluated at 50 ppm loading in the self metathesis of 1-octene (96), at 50 °C under neat conditions, in comparison to symmetrical benchmark second-generation ruthenium catalysts IndII-SIMes, IndII-IMes, GII-SIMes and HGII

• -SIMes (Table 4). Complex 91 was found to give 70% conversion of 1-octene (96) to the desired 7-tetradecene (97) with high selectivity (98% after 1 h, Table 4, entry 1). Moreover, the selectivity did not change over time (Table 4, entry 2). A lower selectivity was observed with IndII-SIMes (Table 4

• high selectivity in the dRRM of cyclopentene 131 was also observed (Scheme 12). Self metathesis of 1-octene (96) was conducted in the presence of 136, 137, 139 and 140, in order to selectively obtain tetradec-7-ene (97). The presence of the N-benzyl substituent was crucial to achieve high yield (up to

Degenerative xanthate transfer to olefins under visible-light photocatalysis

• Atsushi Kaga,
• Xiangyang Wu,
• Joel Yi Jie Lim,
• Hirohito Hayashi,
• Yunpeng Lu,
• Edwin K. L. Yeow and
• Shunsuke Chiba

Beilstein J. Org. Chem. 2018, 14, 3047–3058, doi:10.3762/bjoc.14.283

• ]. Based on these backgrounds, we wondered if the degenerative transfer of xanthates onto olefins could be facilitated by visible-light photocatalysis under milder reaction conditions. We therefore commenced our investigation with the reaction of ethyl ethoxycarbonylmethyl xanthate (1a) and 1-octene (2a

• state of the photocatalyst is a key factor for the energy transfer mechanism. To obtain a detailed mechanistic insight, steady-state photoluminescence (PL) quenching of photocatalyst 8 was examined using xanthate 1a and 1-octene (2a) as potential quenchers (Figure 1). The intensity of the PL peak of

• = 1.25 × 107 M−1s−1 (see Supporting Information File 1). On the other hand, the addition of 1-octene (2a, 40 mM), in place of xanthate 1a, resulted in only a small PL quenching of photocatalyst 8 (<8%, Figure 1B). The time-resolved PL lifetime decay profiles of photocatalyst 8 (25 μM solution in degassed

MoO₃ on zeolites MCM-22, MCM-56 and 2D-MFI as catalysts for 1-octene metathesis

• Hynek Balcar,
• Martin Kubů,
• Naděžda Žilková and
• Mariya Shamzhy

Beilstein J. Org. Chem. 2018, 14, 2931–2939, doi:10.3762/bjoc.14.272

• MoO3 and/or MoO2(acac)2 on MWW zeolites (MCM-22, delaminated MCM-56) and on two-dimensional MFI (all in NH4+ form). The catalysts‘ activities were tested in the metathesis of neat 1-octene (as an example of a longer chain olefin) at 40 °C. Catalysts with 6 wt % or 5 wt % of Mo were used. The acidic

• concentration of the acidic centres resulting in catalysts of moderate activity but with the highest selectivity. Keywords: metathesis; molybdenum oxide; 1-octene; thermal spreading; zeolites; Introduction Molybdenum oxide on silica, alumina or silica-alumina belongs to the well-known and long-time used

• supported MoO3 and/or MoO2(acac)2 on (i) 2D-MFI (and ordinary HZSM-5 for comparison) and similarly on (ii) MCM-56 and its 3D analogue MCM-22 (both in NH4+ form) and examined their activity in the metathesis of neat 1-octene (Scheme 1) under ambient pressure and 40 °C. According to our best knowledge, none

Pd(OAc)₂/Ph₃P-catalyzed dimerization of isoprene and synthesis of monoterpenic heterocycles

• Dominik Kellner,
• Maximilian Weger,
• Andrea Gini and
• Olga García Mancheño

Beilstein J. Org. Chem. 2017, 13, 1807–1815, doi:10.3762/bjoc.13.175

• -butadiene with water followed by reduction to the linear 1-octanol [3][4][5], or the telomerization of 1,3-butadiene with methanol and reduction by the Dow Chemical Company to generate 1-octene [6][7][8][9][10][11][12]. Besides the well-studied case of 1,3-butadiene [5][13][14][15], only few reports for

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

Copper-mediated synthesis of N-alkenyl-α,β-unsaturated nitrones and their conversion to tri- and tetrasubstituted pyridines

• Dimitra Kontokosta,
• Daniel S. Mueller,
• Dong-Liang Mo,
• Wiktoria H. Pace,
• Rachel A. Simpson and
• Laura L. Anderson

Beilstein J. Org. Chem. 2015, 11, 2097–2104, doi:10.3762/bjoc.11.226

• 10–14, the addition of 1.2 equiv of cyclooctadiene (COD), cyclooctene (COE), norbornadiene (NBD), 1-octene, and dibenzylideneacetone (dba) all improved the yield of the Chan–Lam reaction, but COD was most efficient. Having identified optimal conditions for the synthesis of N-cyclohexenylnitrone 8aa

Cross-dehydrogenative coupling for the intermolecular C–O bond formation

• Igor B. Krylov,
• Vera A. Vil’ and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2015, 11, 92–146, doi:10.3762/bjoc.11.13

• , or copper) were performed with cyclohexanone, 2-methylcyclohexanone, cyclohexene, 1-octene, cumene, xylene, dimethylaniline, and dioxane [201]. The enantioselective oxidative coupling of 2,6-dialkylphenyl-β-keto esters and thioesters 215 with tert-butyl hydroxycarbamate 216 was performed using the Cu

Amino acid motifs in natural products: synthesis of O-acylated derivatives of (2S,3S)-3-hydroxyleucine

• Oliver Ries,
• Martin Büschleb,
• Markus Granitzka,
• Dietmar Stalke and
• Christian Ducho

Beilstein J. Org. Chem. 2014, 10, 1135–1142, doi:10.3762/bjoc.10.113

• was transformed into benzyl ester 39 in 97% yield (Scheme 6). Subsequent treatment with commercially available 1-octene and Grubbs 2nd generation catalyst [41] afforded lipidated (2S,3S)-3-hydroxyleucine derivative 40 in 63% yield without any observed homo-coupling of the amino acid. Amino acid 40 was

C2-Alkylation of N-pyrimidylindole with vinylsilane via cobalt-catalyzed C–H bond activation

• Zhenhua Ding and
• Naohiko Yoshikai

Beilstein J. Org. Chem. 2012, 8, 1536–1542, doi:10.3762/bjoc.8.174

• -alkenylation of N-pyrimidylindole, (b) ortho-alkylation of aryl imine, and (c) C2-alkylation of N-pyrimidylindole. Addition of N-pyrimidylindoles to vinylsilanes. Addition of N-pyrimidylindole to norbornene (a) and 1-octene (b). Gram-scale reaction and deprotection of N-pyrimidyl group. Screening of ligands.a

• 20% yield, although the product could not be separated in a pure form. Unfortunately, the present catalytic system was not very effective for C2-alkylation with simple olefins. The reaction of 1a with norbornene (2d) afforded the alkylation product 3ad in 30% yield (Scheme 3a). The reaction of 1

• -octene (2e) was even more sluggish, affording the alkylation product 3ae in only 9% yield (Scheme 3b). Styrene also reacted rather sluggishly to afford only a small amount of the alkylation product (3% as estimated by GC and GCMS), the regiochemistry (branched versus linear) of which has yet to be

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

• phase, was faster than for the batch reaction in toluene, although it was half the rate of the homogeneous system under comparable conditions. This was attributed to the enhanced mass transport properties and the lower viscosity of the medium caused by the presence of scCO2. The residual 1-octene was

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

• . [34]. Using a poly(2-oxazoline)-based amphiphilic copolymer and a RhBr(1,3-dialkylimidazol-2-ylidene-based catalyst, selectivities (n:iso) of ~3 at 40% conversion and an activity (TOF0) of 1630 h−1 in the hydroformylation of 1-octene was observed [35]. Here, we used poly(M1-b-M2)-Rh for the

• hydroformylation of 1-octene in water. For purposes of comparison, the results obtained were compared to those previously obtained with the homogeneous analogue CH3CON(Py)2RhCl(COD) (C1) [9]. As already described [9], the dipyridylamide-based Rh-catalyst C1 is a very fast isomerization catalyst. Consequently

Solvent-free phase-vanishing reactions with PTFE (Teflon^®) as a phase screen

• Kevin Pels and
• Veljko Dragojlovic

Beilstein J. Org. Chem. 2009, 5, No. 75, doi:10.3762/bjoc.5.75

• reaction and the reaction time was longer compared to bromination of liquid substrates (Table 1). The end point of a reaction was determined by removing the delivery tube and weighing the reaction flask. Cyclohexene and 1-octene gave the corresponding dibromo derivatives cleanly and in good yields (Table 1