Access to optically active tetrafluoroethylenated amines based on [1,3]-proton shift reaction

• Yuta Kabumoto,
• Eiichiro Yoshimoto,
• Bing Xiaohuan,
• Masato Morita,
• Motohiro Yasui,
• Shigeyuki Yamada and
• Tsutomu Konno

Beilstein J. Org. Chem. 2024, 20, 2776–2783, doi:10.3762/bjoc.20.233

• published that the asymmetric conjugate addition of 4-methylphenylboronic acid towards (E)-5-bromo-4,4,5,5-tetrafluoro-1-phenyl-2-penten-1-one (8) in the presence of a rhodium catalyst coordinated with (S)-BINAP gave the corresponding Michael adduct 9 in 94% enantiomeric excess (reaction 2, Scheme 1) [22

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

• for integrins which is critical for several diseases. Keywords: biphenyltetracarboxylic acid; homo-coupling; integrin inhibitor; rhodium catalyst; Ullmann-type reaction; Introduction The Ullmann reaction is a coupling reaction of aryl halides using copper, traditionally using metallic copper-bronze

N-Boc-α-diazo glutarimide as efficient reagent for assembling N-heterocycle-glutarimide diads via Rh(II)-catalyzed N–H insertion reaction

• Grigory Kantin,
• Pavel Golubev,
• Alexander Sapegin,
• Alexander Bunev and
• Dmitry Dar’in

Beilstein J. Org. Chem. 2023, 19, 1841–1848, doi:10.3762/bjoc.19.136

• . However, this does not show much advantage over Rh2(esp)2 (0.18 mol %), which gave a preparative yield of 18%. It is important to note that despite the higher cost, the rhodium catalyst offers milder reaction conditions. In the case of some electron-rich substrates, in addition to N–H insertion products 6

Enolates ambushed – asymmetric tandem conjugate addition and subsequent enolate trapping with conventional and less traditional electrophiles

• Péter Kisszékelyi and
• Radovan Šebesta

Beilstein J. Org. Chem. 2023, 19, 593–634, doi:10.3762/bjoc.19.44

• synthesis of enantiomerically enriched cyclobutanes 77 [52]. Their strategy employed a three-component process in which tert-butyl (E)-2-diazo-5-arylpent-4-enoates 74 were treated with the chiral rhodium catalyst C1 to provide enantiomerically enriched bicyclobutanes 75. These highly strained compounds then

Rhodium-catalyzed intramolecular reductive aldol-type cyclization: Application for the synthesis of a chiral necic acid lactone

• Motoyuki Isoda,
• Kazuyuki Sato,
• Kenta Kameda,
• Kana Wakabayashi,
• Ryota Sato,
• Hideki Minami,
• Yukiko Karuo,
• Atsushi Tarui,
• Kentaro Kawai and
• Masaaki Omote

Beilstein J. Org. Chem. 2022, 18, 1642–1648, doi:10.3762/bjoc.18.176

• structural component of the pyrrolizidine alkaloid monocrotaline. Keywords: β-hydroxylactone; intramolecular reductive aldol cyclization; necic acid lactone; rhodium catalyst; Introduction Carbon–carbon bond-forming reactions are among the most important reactions in the synthetic chemistry toolbox and the

Site-selective reactions mediated by molecular containers

• Rui Wang and
• Yang Yu

Beilstein J. Org. Chem. 2022, 18, 309–324, doi:10.3762/bjoc.18.35

• achieved with just the rhodium catalyst, by which in contrast, the fully hydrogenated product was obtained. Other series of intermolecular comparative experiments also showed the selectivity of the hydrogenation for the sterically accessible alkene over other sites and even in the presence of inherently

• by water-soluble cavitands E and F. Site-selective hydrogenation of polyenols mediated by supramolecular encapsulated rhodium catalyst. Site-selective oxidation of steroids using cyclodextrin as the anchoring template. Site-selective oxidations of linear diterpenoids with the help of cage host A

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

• rhodium catalyst in dioxane, in the presence of 2 equivalents of MeOH, at 65 °C, leading to compounds 65 with high diastereomeric ratio. Crude amides 65 were converted into the corresponding pyrrolidines 66 in high yield by stirring at room temperature for 1 h in presence of 2.0 equivalents of LiHMDS

All-carbon [3 + 2] cycloaddition in natural product synthesis

• Zhuo Wang and
• Junyang Liu

Beilstein J. Org. Chem. 2020, 16, 3015–3031, doi:10.3762/bjoc.16.251

• intramolecular [3 + 2] cycloaddition begins with the reaction between the rhodium catalyst Rh(I)LCl and alcohol 110 to give complex A through alcoholysis [50][51] (Scheme 8B). Rh(I)-mediated retro-propargylation of the homopropargyl alcohol A afforded complex B. It undergoes an intramolecular Michael addition

Recent synthesis of thietanes

• Jiaxi Xu

Beilstein J. Org. Chem. 2020, 16, 1357–1410, doi:10.3762/bjoc.16.116

Rhodium-catalyzed reductive carbonylation of aryl iodides to arylaldehydes with syngas

• Zhenghui Liu,
• Peng Wang,
• Zhenzhong Yan,
• Suqing Chen,
• Dongkun Yu,
• Xinhui Zhao and
• Tiancheng Mu

Beilstein J. Org. Chem. 2020, 16, 645–656, doi:10.3762/bjoc.16.61

• pressure, cheap ligand and low metal dosage could significantly improve the practicability in both chemical researches and industrial applications. Keywords: cost-effective ligand; industrial catalysis; reductive carbonylation; rhodium catalyst; syngas; Introduction The exploration of environmentally

Recent developments in photoredox-catalyzed remote ortho and para C–H bond functionalizations

• Rafia Siddiqui and
• Rashid Ali

Beilstein J. Org. Chem. 2020, 16, 248–280, doi:10.3762/bjoc.16.26

• dependence on external oxidants and harsh reaction conditions [83][84]. In this context, in 2014, Fabry et al. reported the use of novel dual photoredox catalytic systems made up of photoredox catalyst 11 and a rhodium catalyst to carry out the Weinreb amide C–H olefination shown in Scheme 1 [85]. By using

Combining the Ugi-azide multicomponent reaction and rhodium(III)-catalyzed annulation for the synthesis of tetrazole-isoquinolone/pyridone hybrids

• Gerardo M. Ojeda,
• Prabhat Ranjan,
• Pavel Fedoseev,
• Lisandra Amable,
• Upendra K. Sharma,
• Daniel G. Rivera and
• Erik V. Van der Eycken

Beilstein J. Org. Chem. 2019, 15, 2447–2457, doi:10.3762/bjoc.15.237

• rhodium catalyst to promote C(sp2)–H activation in the presence of a suitable directing group. The Ugi-azide reaction provides broad molecular diversity and enables the introduction of the tetrazole moiety, which may further assist the catalytic reaction by coordinating the metal center. The scope of the

Intramolecular cascade annulation triggered by rhodium(III)-catalyzed sequential C(sp²)–H activation and C(sp³)–H amination

• Liangliang Song,
• Guilong Tian,
• Johan Van der Eycken and
• Erik V. Van der Eycken

Beilstein J. Org. Chem. 2019, 15, 571–576, doi:10.3762/bjoc.15.52

• , entries 2 and 3). [Ru(p-cymene)Cl2]2 resulted in a very poor yield of 3a (Table 1, entry 4). Alternative rhodium catalyst [RhCp*(CH3CN)3](SbF6)2 gave 17% 2a and 35% 3a (Table 1, entry 5). Without CsOAc under [RhCp*(CH3CN)3](SbF6)2 catalysis, just 29% 2a was isolated (Table 1, entry 6). With CsOPiv instead

Hydroarylations by cobalt-catalyzed C–H activation

• Rajagopal Santhoshkumar and
• Chien-Hong Cheng

Beilstein J. Org. Chem. 2018, 14, 2266–2288, doi:10.3762/bjoc.14.202

• *(C6H6)][B(C6F5)4]2 and LiOAc gave alcohol products 62 with high diastereoselectivity at ambient reaction conditions. The unique nature of cobalt was well presented by its superior reactivity and diastereoselectivity and it outmatched the rhodium catalyst. Different pyrazole derivatives with a wide range

Rh(II)-mediated domino [4 + 1]-annulation of α-cyanothioacetamides using diazoesters: A new entry for the synthesis of multisubstituted thiophenes

• Jury J. Medvedev,
• Ilya V. Efimov,
• Yuri M. Shafran,
• Vitaliy V. Suslonov,
• Vasiliy A. Bakulev and
• Valerij A. Nikolaev

Beilstein J. Org. Chem. 2017, 13, 2569–2576, doi:10.3762/bjoc.13.253

• or 5. Principally, thiophenes 3 and 5 could be derived from the S-ylide B in a somewhat different way, as for instance: coordination E of cyano group in S-ylide with a rhodium catalyst [63] gives rise to zwitterion F with a negative charge located on the rhodium atom, followed by recovery of the

• ylide with the rhodium catalyst. Within the adopted general scheme, the occurrence of thiophenes 4 could be rationalized by partial hydrolysis of carbamates 3 under the reaction conditions with the initial formation of the primary heteroaromatic amines 7. The latter then interact with carbenoids A, to

2-Methyl-2,4-pentanediol (MPD) boosts as detergent-substitute the performance of ß-barrel hybrid catalyst for phenylacetylene polymerization

• Julia Kinzel,
• Daniel F. Sauer,
• Marco Bocola,
• Marcus Arlt,
• Tayebeh Mirzaei Garakani,
• Andreas Thiel,
• Klaus Beckerle,
• Tino Polen,
• Jun Okuda and
• Ulrich Schwaneberg

Beilstein J. Org. Chem. 2017, 13, 1498–1506, doi:10.3762/bjoc.13.148

• that FhuA ΔCVFtev is correctly folded even up to eight weeks. Coupling efficiency of the rhodium catalyst to FhuA ΔCVFtev is more than 90% The rhodium catalyst 1 bearing a maleimide group was attached to FhuA ΔCVFtev for the generation of the biohybrid catalyst [Rh]-FhuA ΔCVFtev 2 as previously

• of the cysteine function of 2 (Cys545) using the fluorescence dye ThioGlo® 1 (fluorescent thiol reagent, Figure S2, Supporting Information File 1). More than 90% of the cysteines are occupied, showing a very high coupling efficiency of the rhodium catalyst. Further, the biohybrid conjugate was

• in 65% polymer with Mn = 5,300 and a high cis-content of 90% (Table 2, entry 1). If the rhodium catalyst is not present, FhuA ΔCVFtev itself is not able to convert the substrate, as expected (Table 2, entry 2). The polymerization reaction of 3 with the biohybrid catalyst 2 is strongly dependent on

Synthesis of 1-indanones with a broad range of biological activity

• Marika Turek,
• Dorota Szczęsna,
• Marek Koprowski and
• Piotr Bałczewski

Beilstein J. Org. Chem. 2017, 13, 451–494, doi:10.3762/bjoc.13.48

• obtained by isomerization of racemic α-arylpropargyl alcohols 161 in the presence of a rhodium catalyst. A high enantioselectivity has been achieved by the use of the chiral bisphosphine ligand (R,R)-160 (Scheme 47). A catalytic cycle of this isomerization is shown in Scheme 48. First, alkoxorhodium 163

The reductive decyanation reaction: an overview and recent developments

• Jean-Marc R. Mattalia

Beilstein J. Org. Chem. 2017, 13, 267–284, doi:10.3762/bjoc.13.30

• ]. Opatz et al. developed the enantioselective syntheses of various alkaloids using the rhodium catalyst developed by Noyori [88] for the asymmetric transfer hydrogenation of imines. Interestingly, imines are formed from unstable α-aminonitrile intermediates which spontaneously eliminate HCN [89][90][91

Unusual reactions of diazocarbonyl compounds with α,β-unsaturated δ-amino esters: Rh(II)-catalyzed Wolff rearrangement and oxidative cleavage of N–H-insertion products

• Valerij A. Nikolaev,
• Jury J. Medvedev,
• Olesia S. Galkina,
• Ksenia V. Azarova and
• Christoph Schneider

Beilstein J. Org. Chem. 2016, 12, 1904–1910, doi:10.3762/bjoc.12.180

• -known for decomposition reactions of diazocarbonyl compounds using Cu and Fe catalysts [29] and in some cases with the employment of Rh-carboxylates as well [30]. Ketoamine F proves to be unstable under the reaction conditions and is oxidized by a rhodium catalyst complex with oxygen producing

Microwave-assisted synthesis of (aminomethylene)bisphosphine oxides and (aminomethylene)bisphosphonates by a three-component condensation

• Erika Bálint,
• Ádám Tajti,
• Anna Dzielak,
• Gerhard Hägele and
• György Keglevich

Beilstein J. Org. Chem. 2016, 12, 1493–1502, doi:10.3762/bjoc.12.146

• ]. (Aminomethylene)bisphosphonates can also be obtained starting from amides, triethyl phosphite and phosphorus oxychloride (Scheme 3a) [37], or in the reaction of amines with diazophosphonate in the presence of a rhodium catalyst (Scheme 3b) [38]. (Aminomethylene)bisphosphine oxides are analogous to (aminomethylene

Conjugate addition–enantioselective protonation reactions

• James P. Phelan and
• Jonathan A. Ellman

Beilstein J. Org. Chem. 2016, 12, 1203–1228, doi:10.3762/bjoc.12.116

• rhodium catalyst binding to the benzoxazole nitrogen 68. Deuterium labeling studies were performed on the system and based on their results a mechanism was proposed in which the stereodetermining step is a rhodium-hydride transfer instead of protonation of an oxo-π-allylrhodium species (Scheme 17

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

• into linear butyraldehyde using a rhodium catalyst immobilized in the aqueous phase by coordination of the famous water-soluble ligand TPPTS (trisodium salt of the trisulfonated triphenylphosphane) [2]. However, while propene is partially soluble in water, terminal alkenes containing more than 6 carbon

Preparation of phosphines through C–P bond formation

• Iris Wauters,
• Wouter Debrouwer and
• Christian V. Stevens

Beilstein J. Org. Chem. 2014, 10, 1064–1096, doi:10.3762/bjoc.10.106

• were isolated as their thiophosphine analogues 135 and 136. Hayashi and co-workers have reported a rhodium-catalyzed phosphination of alkynes 134b using silylphosphines 137 as phosphinating agents (Table 15) [108]. The cationic rhodium catalyst was generated in situ by adding silver triflate to a

Synthesis of five- and six-membered cyclic organic peroxides: Key transformations into peroxide ring-retaining products

• Alexander O. Terent'ev,
• Dmitry A. Borisov,
• Vera A. Vil’ and
• Valery M. Dembitsky

Beilstein J. Org. Chem. 2014, 10, 34–114, doi:10.3762/bjoc.10.6