79299-22-2Relevant academic research and scientific papers
Catalytic oxygen atom transfer promoted by tethered Mo(VI) dioxido complexes onto silica-coated magnetic nanoparticles
Colaiezzi, Roberta,Crucianelli, Marcello,Di Giuseppe, Andrea,Ferella, Francesco,Lazzarini, Andrea,Paolucci, Valentina
, (2021/11/30)
The preparation of three novel active and stable magnetic nanocatalysts for the selective liquid-phase oxidation of several olefins, has been reported. The heterogeneous systems are based on the coordination of cis-MoO2 moiety onto three different SCMNP@Si-(L1-L3) magnetically active supports, functionalized with silylated acylpyrazolonate ligands L1, L2 and L3. Nanocatalysts thoroughly characterized by ATR-IR spectroscopy, TGA and ICP-MS analyses, showed excellent catalytic performances in the oxidation of conjugated or unconjugated olefins either in organic or in aqueous solvents. The good magnetic properties of these catalytic systems allow their easy recyclability, from the reaction mixture, and reuse over five runs without significant decrease in the activity, either in organic or water solvent, demonstrating their versatility and robustness.
Diastereoselective Alkene Hydroesterification Enabling the Synthesis of Chiral Fused Bicyclic Lactones
Shi, Zhanglin,Shen, Chaoren,Dong, Kaiwu
supporting information, p. 18039 - 18042 (2021/11/16)
Palladium-catalysed diastereoselective hydroesterification of alkenes assisted by the coordinative hydroxyl group in the substrate afforded a variety of chiral γ-butyrolactones bearing two stereocenters. Employing the carbonylation-lactonization products as the key intermediates, the route from the alkenes with single chiral center to chiral THF-fused bicyclic γ-lactones containing three stereocenters was developed.
Lewis Base Catalyzed Dioxygenation of Olefins with Hypervalent Iodine Reagents
Pan, Liangkun,Ke, Zhihai,Yeung, Ying-Yeung
supporting information, p. 8174 - 8178 (2021/10/25)
1,2-Diols are extremely useful building blocks in organic synthesis. Hypervalent iodine reagents are useful for the vicinal dihydroxylation of olefins to give 1,2-diols under metal-free conditions, but strongly acidic promoters are often required. Herein, we report a catalytic vicinal dioxygenation of olefins with hypervalent iodine reagents using Lewis bases as catalysts. The conditions are mild and compatible with various functional groups.
Catalytic Diastereo- and Enantioconvergent Synthesis of Vicinal Diamines from Diols through Borrowing Hydrogen
Feng, Wei,Gao, Taotao,Lau, Kai Kiat,Lin, Yamei,Pan, Hui-Jie,Yang, Binmiao,Zhao, Yu
supporting information, p. 18599 - 18604 (2021/08/09)
We present herein an unprecedented diastereoconvergent synthesis of vicinal diamines from diols through an economical, redox-neutral process. Under cooperative ruthenium and Lewis acid catalysis, readily available anilines and 1,2-diols (as a mixture of diastereomers) couple to forge two C?N bonds in an efficient and diastereoselective fashion. By identifying an effective chiral iridium/phosphoric acid co-catalyzed procedure, the first enantioconvergent double amination of racemic 1,2-diols has also been achieved, resulting in a practical access to highly valuable enantioenriched vicinal diamines.
Cobalt-Catalyzed One-Pot Asymmetric Difunctionalization of Alkynes to Access Chiral gem-(Borylsilyl)alkanes
Ge, Shaozhong,You, Yang'en
, p. 20684 - 20688 (2021/08/13)
Enantioselective cobalt-catalyzed one-pot hydrosilylation and hydroboration of terminal alkynes has been developed employing a cobalt catalyst generated from Co(acac)2 and (R,R)-Me-Ferrocelane. A variety of terminal alkynes undergo this asymmetric transformation, affording the corresponding gem-(borylsilyl)alkane products with high enantioselectivity (up to 98 % ee). This one-pot reaction combines (E)-selective hydrosilylation of alkynes and consecutive enantioselective hydroboration of (E)-vinylsilanes with one chiral cobalt catalyst. This protocol represents the most straightforward approach to access versatile chiral gem-(borylsilyl)alkanes from readily available alkynes with commercially available cobalt salt and chiral ligand.
Dendrimer crown-ether tethered multi-wall carbon nanotubes support methyltrioxorhenium in the selective oxidation of olefins to epoxides
Bizzarri, Bruno Mattia,Botta, Lorenzo,Crucianelli, Marcello,Fanelli, Angelica,Ferella, Francesco,Gontrani, Lorenzo,Sadun, Claudia,Saladino, Raffaele
, p. 17185 - 17194 (2020/05/18)
Benzo-15-crown-5 ether supported on multi-wall carbon nanotubes (MWCNTs) by tethered poly(amidoamine) (PAMAM) dendrimers efficiently coordinated methyltrioxorhenium in the selective oxidation of olefins to epoxides. Environmentally friendly hydrogen peroxide was used as a primary oxidant. Up to first and second generation dendrimer aggregates were prepared by applying a divergent PAMAM methodology. FT-IR, XRD and ICP-MS analyses confirmed the effective coordination of methyltrioxorhenium by the benzo-15-crown-5 ether moiety after immobilization on MWCNTs. The novel catalysts converted olefins to the corresponding epoxides in high yield without the use of Lewis base additives, or anhydrous hydrogen peroxide, the catalyst being stable for more than six oxidative runs. In the absence of the PAMAM structure, the synthesis of diols largely prevailed.
Erbium-Catalyzed Regioselective Isomerization-Cobalt-Catalyzed Transfer Hydrogenation Sequence for the Synthesis of Anti-Markovnikov Alcohols from Epoxides under Mild Conditions
Liu, Xin,Longwitz, Lars,Spiegelberg, Brian,T?njes, Jan,Beweries, Torsten,Werner, Thomas
, p. 13659 - 13667 (2020/11/30)
Herein, we report an efficient isomerization-transfer hydrogenation reaction sequence based on a cobalt pincer catalyst (1 mol %), which allows the synthesis of a series of anti-Markovnikov alcohols from terminal and internal epoxides under mild reaction conditions (≤55 °C, 8 h) at low catalyst loading. The reaction proceeds by Lewis acid (3 mol % Er(OTf)3)-catalyzed epoxide isomerization and subsequent cobalt-catalyzed transfer hydrogenation using ammonia borane as the hydrogen source. The general applicability of this methodology is highlighted by the synthesis of 43 alcohols from epoxides. A variety of terminal (23 examples) and 1,2-disubstituted internal epoxides (14 examples) bearing different functional groups are converted to the desired anti-Markovnikov alcohols in excellent selectivity and yields of up to 98%. For selected examples, it is shown that the reaction can be performed on a preparative scale up to 50 mmol. Notably, the isomerization step proceeds via the most stable carbocation. Thus, the regiochemistry is controlled by stereoelectronic effects. As a result, in some cases, rearrangement of the carbon framework is observed when tri-and tetra-substituted epoxides (6 examples) are converted. A variety of functional groups are tolerated under the reaction conditions even though aldehydes and ketones are also reduced to the respective alcohols under the reaction conditions. Mechanistic studies and control experiments were used to investigate the role of the Lewis acid in the reaction. Besides acting as the catalyst for the epoxide isomerization, the Lewis acid was found to facilitate the dehydrogenation of the hydrogen donor, which enhances the rate of the transfer hydrogenation step. These experiments additionally indicate the direct transfer of hydrogen from the amine borane in the reduction step.
Site-Selective Mono-Oxidation of 1,2-Bis(boronates)
Yan, Lu,Morken, James P.
, p. 3760 - 3763 (2019/05/24)
Site-selective oxidation of vicinal bis(boronates) is accomplished through the use of trimethylamine N-oxide in 1-butanol solvent. The reaction occurs with good efficiency and selectivity across a range of substrates, providing 2-hydro-1-boronic esters which are shown to be versatile intermediates in the synthesis of chiral building blocks.
Reductive α-borylation of α,β-unsaturated esters using NHC-BH3 activated by I2 as a metal-free route to α-boryl esters
Radcliffe, James E.,Fasano, Valerio,Adams, Ralph W.,You, Peiran,Ingleson, Michael J.
, p. 1434 - 1441 (2019/02/06)
Useful α-boryl esters can be synthesized in one step from α,β-unsaturated esters using just a simple to access NHC-BH3 (NHC = N-heterocyclic carbene) and catalytic I2. The scope of this reductive α-borylation methodology is excellent and includes a range of alkyl, aryl substituted and cyclic and acyclic α,β-unsaturated esters. Mechanistic studies involving reductive borylation of a cyclic α,β-unsaturated ester with NHC-BD3/I2 indicated that concerted hydroboration of the alkene moiety in the α,β-unsaturated ester proceeds instead of a stepwise process involving initial 1,4-hydroboration; this is in contrast to the recently reported reductive α-silylation. The BH2(NHC) unit can be transformed into electrophilic BX2(NHC) moieties (X = halide) and the ester moiety can be reduced to the alcohol with the borane unit remaining intact to form β-boryl alcohols. The use of a chiral auxiliary, 8-phenylmenthyl ester, also enables effective stereo-control of the newly formed C-B bond. Combined two step ester reduction/borane oxidation forms diols, including excellent e.e. (97%) for the formation of S-3-phenylpropane-1,2-diol. This work represents a simple transition metal free route to form bench stable α-boryl esters from inexpensive starting materials.
Synthesis of Seven-Membered Benzolactones by Nickel-Catalyzed C?H Coupling of Benzamides with Oxetanes
Xu, Shibo,Takamatsu, Kazutaka,Hirano, Koji,Miura, Masahiro
supporting information, p. 9400 - 9404 (2019/03/26)
A NiCl2(PEt3)2-catalyzed regioselective C?H coupling of 8-aminoquinoline-derived benzamides with oxetanes has been developed. The reaction proceeds with concomitant removal of the 8-aminoquinoline auxiliary to directly for
