6713-49-1Relevant academic research and scientific papers
Stereodivergent synthesis of alkenes by controllable syn-/anti-fragmentation of β-hydroxysulfonyl intermediates
Górski, Bartosz,Basiak, Dariusz,Grzesiński, ?ukasz,Barbasiewicz, Micha?
supporting information, p. 7660 - 7663 (2019/08/30)
The reduction of the carbonyl group in acylated trifluoroethyl alkanesulfonates follows the Felkin-Ahn selectivity, and the so-formed diastereomeric β-hydroxysulfonyl intermediates undergo syn- and anti-fragmentation, depending on the reaction conditions. In effect, isomeric E- and Z-alkenes are formed in a stereodivergent manner, which mimics the mechanistic manifold of the Peterson olefination.
Highly Selective Hydrogenation of Aromatic Ketones and Phenols Enabled by Cyclic (Amino)(alkyl)carbene Rhodium Complexes
Wei, Yu,Rao, Bin,Cong, Xuefeng,Zeng, Xiaoming
supporting information, p. 9250 - 9253 (2015/08/11)
Air-stable Rh complexes ligated by strongly σ-donating cyclic (amino)(alkyl)carbenes (CAACs) show unique catalytic activity for the selective hydrogenation of aromatic ketones and phenols by reducing the aryl groups. The use of CAAC ligands is essential for achieving high selectivity and conversion. This method is characterized by its good compatibility with unsaturated ketones, esters, carboxylic acids, amides, and amino acids and is scalable without detriment to its efficiency.
Carbonylation of organic halides with carbon monoxide mediated by samarium diiodide. Improvement and mechanistic investigations
Tomisaka, Yuri,Harato, Nami,Sato, Masahiro,Nomoto, Akihiro,Ogawa, Akiya
, p. 1444 - 1446 (2007/10/03)
Under an atmospheric pressure of carbon monoxide, photoinduced reductive carbonylation of organic halides (RX) with samarium diiodide (SmI2) occurs to afford the corresponding unsymmetrical ketones (RC(O)CH2R) in good yields. Mechanistic insight into this carbonylation, especially the pathway for the generation of an acylsamarium species (RC(O)SmI2) as a key intermediate, is also investigated in detail.
A novel photoinduced reduction system of low-valent samarium species: Reduction of organic halides and chalcogenides, and its application to carbonylation with carbon monoxide
Sumino, Yukihito,Harato, Nami,Tomisaka, Yuri,Ogawa, Akiya
, p. 10499 - 10508 (2007/10/03)
Visible light irradiation is found to enhance the reducing ability of samarium diiodide (SmI2) dramatically. Organic halides (RCl, RBr, RI) and chalcogenides (RSPh, RSePh, RTePh) are smoothly reduced to the corresponding hydrocarbons by using this SmI2-hv system. The photoactivation can be also applied to ytterbium diiodide (YbI2) successfully. When the reduction of alkyl chlorides (RCl) by using the SmI 2-hv system is conducted under the pressure of carbon monoxide, unsymmetric ketones (RC(O)CH2R) are obtained as carbonylating products. A mechanistic pathway may involve the formation of acylsamarium species (RC(O)SmI2), which undergo dimerization, followed by reduction with SmI2, leading to the unsymmetric ketones.
New coupling reactions of some acyl chlorides with samarium diiodide in the presence of samarium: Carbinols from three acyl units
Clausen, Christian,Weidner, Ingo,Butenschoen, Holger
, p. 3799 - 3806 (2007/10/03)
A mixture of samarium(II) iodide and samarium can induce a coupling reaction of three molecules of alkanoyl halide to give trialkylcarbinols of 2-hydroxy-1,3-diones. When aliphatic, unbranched alkanoyl chlorides are used, this new coupling reaction provides trimeric products as the main reaction products. Tetrahydropyran (THP) proved superior as the solvent because no ring-opening and subsequent reaction with the alkanoyl halides was observed under the reaction conditions, unlike when THF was used. Wiley-VCH Verlag GmbH, 2000.
The reduction of α-silyloxy ketones using phenyldimethylsilyllithium
Fleming, Ian,Roberts, Richard S.,Smith, Stephen C.
, p. 1215 - 1228 (2007/10/03)
Phenyldimethylsilyllithium reacts with acyloin silyl ethers RCH(OSiMe3)COR 8 to give regiodefined silyl enol ethers RCH=C(OSiMe2Ph)R 9, and hence by hydrolysis ketones RCH2COR 10. The yields can be high but are usually moderate. The mechanism of this reduction is established to involve a Brook rearrangement (Scheme 6) rather than a Peterson elimination (Scheme 1). Although the mechanism appears to be the same in each case, the stereochemistries of the silyl enol ethers 9 are opposite in sense in the aromatic series (R = Ph, Scheme 7) and the aliphatic series (R = cyclohexyl, Scheme 8), with the major aromatic silyl enol ether being the thermodynamically less stable isomer E-PhCH=C(OSiMe2Ph)Ph E-9aa, and the major aliphatic silyl enol ether being the thermodynamically more stable isomer Z-c-C6H11CH= C(OSiMe2Ph)-c-C6H11 Z-9ba. This is a consequence of anomalous anti-Felkin attack in the aromatic series. The reaction with the silyl ether ButCH(OSiMe3)COPh 13b is normal in giving Z-ButCH= C(OSiMe2Ph)Ph Z-38 (Scheme 11), but reduction of the silyl ether 8a with lithium aluminium hydride is also anti-Felkin giving with high selectivity the meso diol PhCH(OH)CH(OH)Ph 39. The reaction between Phenyldimethylsilyllithium and the acyloin silyl ether 8d (R = But) does not give the ketone ButCH2COBut, but gives instead the anti-Felkin meso diol ButCHOHCHOHBut 40 also with high selectivity (Scheme 12). Silyllithium and some related reagents react with trifluoromethyl ketones 46 and 48 to give α,α-difluoro silyl enol ethers 47 and 49 (Scheme 14).
Reductive couplings of acid chlorides mediated by SmI2
Collin,Dallemer,Namy,Kagan
, p. 7407 - 7410 (2007/10/02)
Reductive couplings of acid chlorides and of acid chlorides with aldehydes or ketones in presence of an excess of SmI2 produce ketones in moderate to good yields.
