(E,Z)-1,1,1,4,4,4-Hexafluorobut-2-enes: hydrofluoroolefins halogenation/dehydrohalogenation cascade to reach new fluorinated allene

• Nataliia V. Kirij,
• Andrey A. Filatov,
• Yurii L. Yagupolskii,
• Sheng Peng and
• Lee Sprague

Beilstein J. Org. Chem. 2024, 20, 452–459, doi:10.3762/bjoc.20.40

• bond in butenes 1a,b have been presented in the literature. First, Crimmin et al. investigated the reaction of an aluminum(I) complex with fluoroalkenes. Unlike all the presented fluoroolefins, the reaction of the Al(I) complex with (Z)-butene 1b did not allow isolating the intermediate organoaluminum

Application of N-heterocyclic carbene–Cu(I) complexes as catalysts in organic synthesis: a review

• Nosheen Beig,
• Varsha Goyal and
• Raj K. Bansal

Beilstein J. Org. Chem. 2023, 19, 1408–1442, doi:10.3762/bjoc.19.102

• of imidazolium salt 109 (R1 = iBu) resulted in the highest level of stereoinduction for the conjugate addition of EtMgBr to 3-methylcyclohexenone. 2.2.2 Reaction with organoaluminum reagents: Hoveyda and co-workers [60] investigated the NHC–copper-catalyzed asymmetric conjugate addition of alkyl- and

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

• %) but low trans/cis selectivity (Scheme 11). Organoaluminum reagents (Me3Al, Et3Al) were also compatible with the reaction, however, they gave lower yields than the corresponding organozincs. The authors have also shown that these products are suitable for forming [6,7]-bicyclic adducts. Conjugate

α-Ketol and α-iminol rearrangements in synthetic organic and biosynthetic reactions

• Scott Benz and
• Andrew S. Murkin

Beilstein J. Org. Chem. 2021, 17, 2570–2584, doi:10.3762/bjoc.17.172

• silyl ethers. Ooi et al. utilized an axially chiral organoaluminum Lewis acid catalyst (18) to convert a series of α,α-dialkyl-α-siloxyaldehydes 16 to α-siloxyketones 17 in high yields and >74% ee (Figure 5) [7]. This reaction is noteworthy for its tolerance of silyl protecting groups, which are

• catalyzed by Al(III) or Sc(III) liganded by 11. Ligand 11: for 9, m = 1 and Ar = 2,6-iPr2C6H3; for 12, m = 1 and Ar = 2,6-Me2C6H3; and for 14, m = 0 and Ar = 2,4,6-iPr3C6H2. Asymmetric rearrangement of α,α-dialkyl-α-siloxyaldehydes 16 to α-siloxyketones 17 catalyzed by chiral organoaluminum Lewis acid 18

Synthesis of polydicyclopentadiene using the Cp₂TiCl₂/Et₂AlCl catalytic system and thin-layer oxidation of the polymer in air

• Zhargolma B. Bazarova,
• Ludmila S. Soroka,
• Alex A. Lyapkov,
• Мekhman S. Yusubov and
• Francis Verpoort

Beilstein J. Org. Chem. 2019, 15, 733–745, doi:10.3762/bjoc.15.69

• catalytic activity of the Cp2TiCl2/organoaluminum compound is determined by the molar ratio of the components of the catalytic system [15]. The rate of transformation in the system depends both on the Al:Ti molar ratio and on the temperature [16]. UV spectra of toluene solutions of Cp2TiCl2 and AlEt2Cl

• (Figure 1) in the visible region at ambient temperature clearly demonstrate that during the first minute of the reaction an intermediate compound is formed, which gradually decomposes with formation of the blue complex [15][16]. The complexation between the organoaluminum compound and Cp2TiCl2 was further

• study reports regularities of DCPD polymerization in a toluene solution applying a catalytic system consisting of Cp2TiCl2 and AlEt2Cl. It was demonstrated that the use of an excessive amount of organoaluminum leads to the formation of stable charged blue complexes which initiate the cationic

Silanediol versus chlorosilanol: hydrolyses and hydrogen-bonding catalyses with fenchole-based silanes

• Falco Fox,
• Jörg M. Neudörfl and
• Bernd Goldfuss

Beilstein J. Org. Chem. 2019, 15, 167–186, doi:10.3762/bjoc.15.17

• , BIFOL, Figure 1) [52][54] and it´s derivative, the chiral chlorophosphite ligand 6 (BIFOP-Cl, Figure 1), e.g., in Cu-catalyzed 1,4-additions [53], in Pd-catalyzed alkyl–aryl cross coupling reactions [55][56], as well as for organoaluminum fencholate reagents [57]. Unexpected stability against hydrolysis

Recent advances in copper-catalyzed asymmetric coupling reactions

• Fengtao Zhou and
• Qian Cai

Beilstein J. Org. Chem. 2015, 11, 2600–2615, doi:10.3762/bjoc.11.280

• other metals (Pd, Mo, and Ir), copper-catalyzed allylic substitution reactions allow the use of nonstabilized nucleophiles including organomagnesium, organoaluminum, organozinc and organoborane reagents. Moreover, copper-catalyzed allylic substitution reactions usually proceed with high SN2

Copper-catalyzed arylation of alkyl halides with arylaluminum reagents

• Bijay Shrestha and
• Ramesh Giri

Beilstein J. Org. Chem. 2015, 11, 2400–2407, doi:10.3762/bjoc.11.261

• excellent yields. Keywords: alkylation; arylalkanes; copper; cross-coupling; organoaluminum; Introduction Cross-coupling reactions represent one of the most important transformation for carbon–carbon (C–C) bond formation in organic synthesis [1][2][3][4][5][6][7][8][9]. These reactions, typically

• inexpensive and earth-abundant metal. Organoaluminum reagents can be prepared directly from metallic aluminum [13][14][15], which further highlights the potential scope of these reagents in organic synthesis. However, despite extensive investigations and applications of organometallic reagents of Si, B, Mg

• , intramolecular coordination to Al also enables the couplings of alkylalanes with organo halides [21]. Knochel [15] and Hoveyda [22] have also shown that organoaluminum reagents are capable of transmetalating to Cu-salts. Inspired by these literature reports and our recent investigations, we envisioned that

An unusually stable chlorophosphite: What makes BIFOP–Cl so robust against hydrolysis?

• Roberto Blanco Trillo,
• Jörg M. Neudörfl and
• Bernd Goldfuss

Beilstein J. Org. Chem. 2015, 11, 313–322, doi:10.3762/bjoc.11.36

• ) were employed in enantioselective organozinc catalysis reactions [23][24][25][26], umpolung catalysis [27] and in organoaluminum [17] and chiral n-butyllithium aggregates [28][29][30][31][32][33]. The chlorophosphite BIFOP-Cl (1) is air-stable and very resistant to hydrolysis (Scheme 2) [13][15]. The

• (1) with water (BP86/def-SV(P)). Transition state structure for the reaction of O-BIFOP–Cl (3) with water (BP86/def-SV(P)). Fenchyl-based ligands used as building blocks for phosphorous ligands or organoaluminum reagents. Reaction of BIFOP–Cl (1) to BIFOP–(O)H (2) and of O–BIFOP–Cl (3) yielding O

Synthesis of chiral N-phosphinyl α-imino esters and their application in asymmetric synthesis of α-amino esters by reduction

• Yiwen Xiong,
• Haibo Mei,
• Lingmin Wu,
• Jianlin Han,
• Yi Pan and
• Guigen Li

Beilstein J. Org. Chem. 2014, 10, 653–659, doi:10.3762/bjoc.10.57

• used for the asymmetric synthesis of α-amino esters through reduction. The reduction condition scan was firstly focused on the examination of reductants. A number of reductants, including Hantzsch ester, silanes, organoaluminum and boranes were tested in the system. Unfortunately, silanes failed to

The chemistry of bisallenes

• Henning Hopf and
• Georgios Markopoulos

Beilstein J. Org. Chem. 2012, 8, 1936–1998, doi:10.3762/bjoc.8.225

• and terminally cycloalkylated bisallenes have also been obtained by another approach starting from C6-derived precursors: the alkylation of diacetylene glycol esters with organoaluminum reagents. The example shown in Scheme 7 is typical. Treatment of diacetate 47 with triethylaluminum in ether under