Palladium-catalyzed three-component radical-polar crossover carboamination of 1,3-dienes or allenes with diazo esters and amines

• Geng-Xin Liu,
• Xiao-Ting Jie,
• Ge-Jun Niu,
• Li-Sheng Yang,
• Xing-Lin Li,
• Jian Luo and
• Wen-Hao Hu

Beilstein J. Org. Chem. 2024, 20, 661–671, doi:10.3762/bjoc.20.59

• process (Scheme 1c). In this process, the hybrid α-ester alkylpalladium radical species from diazo ester adds to the double bond of 1,3-dienes or allenes, followed by the allylpalladium radical-polar crossover path. As with the classical Tsuji–Trost reaction, a subsequent nucleophilic attack of an amine

• [32][33][34][35][36][37][59][60][61][62], upon the loss of dinitrogen. The radical I further adds to the terminal position of 1,3-butadiene (2a) to produce hybrid allylPd radical II, which would exist in equilibrium with π-allyl complex III. Following the classical Tsuji–Trost reaction mechanism, a

Vicinal ketoesters – key intermediates in the total synthesis of natural products

• Marc Paul Beller and
• Ulrich Koert

Beilstein J. Org. Chem. 2022, 18, 1236–1248, doi:10.3762/bjoc.18.129

• ]. The major trans-isomer 73 was further converted to the natural products corynoxine and rychnophylline. The minor cis-isomer 74 was used in an intramolecular Tsuji–Trost reaction, where the ketoester served as a nucleophile, which build up the piperidine ring and selectively set the desired cis

• ) [25]. Intramolecular photoreduction of an α-ketoester in the synthesis of (rac)-isoretronecanol (69) [26]. α-Ketoester as nucleophile in a Tsuji–Trost reaction in the synthesis of (rac)-corynoxine (76) [27]. Mannich reaction of an α-ketoester in the synthesis of (+)-gracilamine (83) [28

Regioselectivity of the S_EAr-based cyclizations and S_EAr-terminated annulations of 3,5-unsubstituted, 4-substituted indoles

• Jonali Das and
• Sajal Kumar Das

Beilstein J. Org. Chem. 2022, 18, 293–302, doi:10.3762/bjoc.18.33

• published in the last decade [5][6][7], this is the first time the regioselectivity of the SEAr-based/terminated cyclization and annulation reactions of 3,5-unsubstituted, 4-substituted indolesis is sytematized as a dedicated topic. Discussion The Tsuji–Trost reaction serves as a powerful tool in

• constructing carbon–carbon and carbon–heteroatom bonds in organic synthesis [8][9][10]. In the course of their diversity-oriented synthesis of indole-based peri-annulated compounds, You and co-workers in 2013 reported the intramolecular Tsuji–Trost reaction of indolyl allyl carbonates 1 under the catalysis of

Switchable selectivity in Pd-catalyzed [3 + 2] annulations of γ-oxy-2-cycloalkenones with 3-oxoglutarates: C–C/C–C vs C–C/O–C bond formation

• Yang Liu,
• Julie Oble and
• Giovanni Poli

Beilstein J. Org. Chem. 2019, 15, 1107–1115, doi:10.3762/bjoc.15.107

• , resonance-stabilized acetamides and cyclic α,β-unsaturated-γ-oxicarbonyl derivatives are used as bis-nucleophile and bis-electrophile partners, respectively. This process involves an intermolecular Pd(0)-catalyzed C-allylation (Tsuji–Trost reaction)/intramolecular nitrogen 1,4-addition sequence (Scheme 1

D-Fructose-based spiro-fused PHOX ligands: synthesis and application in enantioselective allylic alkylation

• Michael R. Imrich,
• Jochen Kraft,
• Cäcilia Maichle-Mössmer and
• Thomas Ziegler

Beilstein J. Org. Chem. 2018, 14, 2082–2089, doi:10.3762/bjoc.14.182

• acetate as model substrate. Keywords: Fürst–Plattner rule; oxazoline; Ritter reaction; Tsuji–Trost reaction; Ullmann coupling; Introduction The vast majority of biologically active compounds like vitamins and natural products occur as single enantiomers in nature. Usually only one enantiomer generates

• protective groups (5b) and one with ester groups (5i). As a model system for the Pd-catalyzed Tsuji–Trost reaction we chose diphenylallyl acetate 15 (Scheme 7) with dimethyl malonate. The latter allylic alkylation is well investigated and has often been used as a benchmark test for the selectivity of novel

• -fused PHOX ligands. The described ligands can be prepared from literature-known carbohydrate derivatives in two steps. Preliminary tests of the spiro-fused PHOX ligands in Tsuji–Trost reaction showed promising results. Different metal complexes as well as further application of the ligands in asymmetric

Recent applications of chiral calixarenes in asymmetric catalysis

• Mustafa Durmaz,
• Erkan Halay and
• Selahattin Bozkurt

Beilstein J. Org. Chem. 2018, 14, 1389–1412, doi:10.3762/bjoc.14.117

• phosphinoferrocenyl-substituted calixarene ligands 27–29. Asymmetric coupling reaction of aryl boronates and aryl halides in the presence of calixarene mono and di(ferrocenylphosphine) ligands 27 and 28. Asymmetric allylic alkylation in the presence of calix[4]arene ligand (S,S)-29. Asymmetric Tsuji–Trost reaction in

Et₃B-mediated and palladium-catalyzed direct allylation of β-dicarbonyl compounds with Morita–Baylis–Hillman alcohols

• Ahlem Abidi,
• Yosra Oueslati and
• Farhat Rezgui

Beilstein J. Org. Chem. 2016, 12, 2402–2409, doi:10.3762/bjoc.12.234

• Tsuji–Trost reaction involving, as substrates, allyl carboxylates [2], carbonates [3], and phosphates [4]. Obviously, the direct nucleophilic allylic substitution of allyl alcohols is a more attractive process especially from an economical and environmental point of view [5], as water, generated by this

Modular synthesis of the pyrimidine core of the manzacidins by divergent Tsuji–Trost coupling

• Sebastian Bretzke,
• Stephan Scheeff,
• Felicitas Vollmeyer,
• Friederike Eberhagen,
• Frank Rominger and
• Dirk Menche

Beilstein J. Org. Chem. 2016, 12, 1111–1121, doi:10.3762/bjoc.12.107

• -metathesis of a challenging homoallylic urea substrate, which proceeds in good yields in the presence of an organic phosphoric acid. Keywords: cross-metathesis; natural products; pyrimidines; Tsuji–Trost reaction; synthetic methods; Introduction Chiral pyrimidine motifs constitute prevalent structural

• ][30][31], we became interested to devise a novel and a more versatile route to the central heterocyclic core of these marine metabolites. The method is based on a late-stage diversification strategy involving a Tsuji–Trost reaction of the urea-type joint precursor 5. In contrast to existing routes

Spiro-fused carbohydrate oxazoline ligands: Synthesis and application as enantio-discrimination agents in asymmetric allylic alkylation

• Jochen Kraft,
• Martin Golkowski and
• Thomas Ziegler

Beilstein J. Org. Chem. 2016, 12, 166–171, doi:10.3762/bjoc.12.18

• of tertiary carbon stereocenters, remains an ongoing challenge. Over the last decades though, transition metal-catalyzed reactions like the asymmetric allylic alkylation (Tsuji–Trost reaction) have evolved into one of the more powerful tools for synthesizing such tertiary stereocenters [7][8]. As a

Inherently chiral calix[4]arenes via oxazoline directed ortholithiation: synthesis and probe of chiral space

• Simon A. Herbert,
• Laura J. van Laeren,
• Dominic C. Castell and
• Gareth E. Arnott

Beilstein J. Org. Chem. 2014, 10, 2751–2755, doi:10.3762/bjoc.10.291

• inherent chirality on the calix[4]arenes can be also be used to drive asymmetric transformations/reactions. Experimental See Supporting Information File 1. N,S Ligands. Synthesis of inherently chiral calix[4]arenes. Synthesis of tert-butyloxazoline calix[4]arenes. Tsuji–Trost reaction. Results of

• ortholithiation study.a Results of the Tsuji–Trost reaction. Supporting Information Experimental details and characterization data for all products; determination of enantiomeric ratios and determination of major calix[4]arene diastereomer. Supporting Information File 480: Synthetic procedures and spectral data

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

• that the addition of randomly modified β-cyclodextrin (RAME-β-CD) in aqueous medium could have a beneficial impact on the catalytic performances of phosphane-based aggregates in the Pd-catalyzed cleavage of allyl carbonates (Tsuji–Trost reaction). The RAME-β-CD/phosphane supramolecular interactions

• carbonates (Tsuji–Trost reaction) and four amphiphilic phosphanes as aggregate-building blocks. The RAME-β-CD/phosphane interaction and its consequence on the catalytic results are discussed. Results and Discussion To expand the scope of the CD/amphiphilic phosphane combination in aqueous-phase

• per mole of palladium and per hour in the early stage of the reaction (20–40% of conversion). Tsuji–Trost reaction mediated by a phosphane-based micelle/RAME-β-CD combination. Supporting Information Supporting Information File 302: Experimental procedures and characterization of the supramolecular

Sordarin, an antifungal agent with a unique mode of action

• Huan Liang

Beilstein J. Org. Chem. 2008, 4, No. 31, doi:10.3762/bjoc.4.31

• sordarin [17] in 2004 and 2006, respectively. Both Kato’s and Mander’s syntheses employed intramolecular Diels-Alder cyclizations to construct the norbornene-like framework, while an intramolecular Pd catalyzed Tsuji-Trost reaction was utilized by the Narasaka group to build the diterpene core. Kato’s

• reaction of sordaricin ester 34 with glycosyl fluoride 35. Unlike previous syntheses, the present one utilized an intramolecular Tsuji-Trost reaction [29] of allylic carbonate 37 to build the core of sordaricin 36. In turn, compound 37 was prepared from bicyclic ketone 38, which was derived from

• ). Selective cleavage of the TBS group and PCC oxidation surrendered ketone 49. Diastereoselective addition of vinylmagnesium chloride and exchange of the enol protecting group gave allylic alcohol 50. The substrate 51 for the Tsuji-Trost reaction was prepared by carbethoxylation of the allylic alcohol and