Palladium-catalyzed hydrodehalogenation of aryl halides using paraformaldehyde as the hydride source: high-throughput screening by paper-based colorimetric iodide sensor

Paraformaldehyde was employed as a hydride source in the palladium-catalyzed hydrodehalogenation of aryl iodides and bromides. High throughput screening using a paper-based colorimetric iodide sensor (PBCIS) showed that Pd(OAc)₂ and Cs₂CO₃ were the best catalyst and base, respectively. Aryl iodides and bromides were hydrodehalogenated to produce the reduced arenes using Pd(OAc)₂ and Pd(PPh₃)₄ catalyst. This catalytic system showed good functional group tolerance. In addition, it was found that paraformaldehyde is the hydride source and the reducing agent for the formation of palladium nanoparticles.     

Palladium-catalyzed C–S bond formation by using N-amido imidazolium salts as ligands

N-Amido imidazolium salt was employed as a ligand in the palladium-catalyzed cross-coupling reaction of aryl halides and thiols, and showed good activity in the formation of thioether. The best combination for the coupling with aryl bromides was N-amido imidazolium salt 2 and NaHMDS, and that for the coupling with aryl iodides was N-amido imidazolium salt 1 and KO^tBu. The coupling reactions were conducted in the presence of Pd(OAc)₂ (1 mol %) in DMSO at 80 °C for 12 h.     

Domino reactions in water for the stereoselective synthesis of novel spiro dihydro-2′H-[indene-2,3′-thiophen]-1(3H)-ones with three contiguous stereocenters

The domino reactions of (E)-2-(aryl)-2,3-dihydro-1H-inden-1-ones and 1,4-dithiane-2,5-diol in the presence of triethylamine in water stereoselectively afforded a library of 2′-(aryl)-4′-hydroxy-4′,5′-dihydro-2′H-spiro[indene-2,3′-thiophen]-1(3H)-ones. This transformation presumably proceeds via the generation of 2-mercaptoacetaldehyde from 1,4-dithiane-2,5-diol followed by Michael addition–intramolecular aldol sequence with C–C and C–S bond formations and creation of three contiguous stereocenters in a one-pot operation.     

硅胶功能化的N-丙哌嗪固载钯纳米粒子作为有效的多相催化剂用于氰化反应(英文)

An efficient heterogeneous Pd catalytic system has been developed, based on immobilization of Pd nanoparticles (PNPs) on a silica-bonded N-propylpiperazine (SBNPP) substrate. The SBNPP substrate effectively stabilizes the PNPs and improves their stability against aggregation. The catalytic activity of this catalyst was investigated in the cyanation of aryl halides with K4[Fe(CN)6 ] as the cyanide source. The catalyst could be recycled several times without appreciable loss of catalytic activity.     

Solvent-Free Mechanochemical Synthesis of Aryl Glycosides[ 1 ]

Aryl glycosides have been prepared from a range of readily available glycosyl halides by a solvent-free mechanochemical procedure employing a planetary ball mill in excellent yields. Besides being a solvent-free reaction, the procedure has been successful in eliminating the need for employing any phase-transfer catalyst in the reaction.     

Chiral Fluorinated α‐Sulfonyl Carbanions: Enantioselective Synthesis and Electrophilic Capture,Racemization Dynamics,and Structure

Enantiomerically pure triflones R¹CH(R²)SO₂CF₃ have been synthesized starting from the corresponding chiral alcohols via thiols and trifluoromethylsulfanes. Key steps of the syntheses of the sulfanes are the photochemical trifluoromethylation of the thiols with CF₃Hal (Hal=halide) or substitution of alkoxyphosphinediamines with CF₃SSCF₃. The deprotonation of RCH(Me)SO₂CF₃ (R=CH₂Ph, iHex) with nBuLi with the formation of salts [RC(Me)? SO₂CF₃]Li and their electrophilic capture both occurred with high enantioselectivities. Displacement of the SO₂CF₃ group of (S)‐MeOCH₂C(Me)(CH₂Ph)SO₂CF₃ (95 % ee) by an ethyl group through the reaction with AlEt₃ gave alkane MeOCH₂C(Me)(CH₂Ph)Et of 96 % ee. Racemization of salts [R¹C(R²)SO₂CF₃]Li follows first‐order kinetics and is mainly an enthalpic process with small negative activation entropy as revealed by polarimetry and dynamic NMR (DNMR) spectroscopy. This is in accordance with a C_α? S bond rotation as the rate‐determining step. Lithium α‐(S)‐trifluoromethyl‐ and α‐(S)‐nonafluorobutylsulfonyl carbanion salts have a much higher racemization barrier than the corresponding α‐(S)‐tert‐butylsulfonyl carbanion salts. Whereas [PhCH₂C(Me)SO₂tBu]Li/DMPU (DMPU = dimethylpropylurea) has a half‐life of racemization at ?105 °C of 2.4 h, that of [PhCH₂C(Me)SO₂CF₃]Li at ?78 °C is 30 d. DNMR spectroscopy of amides (PhCH₂)₂NSO₂CF₃ and (PhCH₂)N(Ph)SO₂CF₃ gave N? S rotational barriers that seem to be distinctly higher than those of nonfluorinated sulfonamides. NMR spectroscopy of [PhCH₂C(Ph)SO₂R]M (M=Li, K, NBu₄; R=CF₃, tBu) shows for both salts a confinement of the negative charge mainly to the C_α atom and a significant benzylic stabilization that is weaker in the trifluoromethylsulfonyl carbanion. According to crystal structure analyses, the carbanions of salts {[PhCH₂C(Ph)SO₂CF₃]Li? L }₂ ( L =2 THF, tetramethylethylenediamine (TMEDA)) and [PhCH₂C(Ph)SO₂CF₃]NBu₄ have the typical chiral C_α? S conformation of α‐sulfonyl carbanions, planar C_α atoms, and short C_α? S bonds. Ab initio calculations of [MeC(Ph)SO₂tBu]^? and [MeC(Ph)SO₂CF₃]^? showed for the fluorinated carbanion stronger n_C→σ* and n_O→σ* interactions and a weaker benzylic stabilization. According to natural bond orbital (NBO) calculations of [R¹C(R²)SO₂R]^? (R=tBu, CF₃) the n_C→σ*_{S? R} interaction is much stronger for R=CF₃. Ab initio calculations gave for [MeC(Ph)SO₂tBu]Li ? 2 Me₂O an O,Li,C_α contact ion pair (CIP) and for [MeC(Ph)SO₂CF₃]Li ? 2 Me₂O an O,Li,O CIP. According to cryoscopy, [PhCH₂C(Ph)SO₂CF₃]Li, [iHexC(Me)SO₂CF₃]Li, and [PhCH₂C(Ph)SO₂CF₃]NBu₄ predominantly form monomers in tetrahydrofuran (THF) at ?108 °C. The NMR spectroscopic data of salts [R¹(R²)SO₂R³]Li (R³=tBu, CF₃) indicate that the dominating monomeric CIPs are devoid of C_α? Li bonds.     

Diastereo‐ and Regioselective Addition of Thioamide Dianions to Imines and Aziridines: Synthesis of N‐Thioacyl‐1,2‐diamines and N‐Thioacyl‐1,3‐diamines

Addition reactions of thioamide dianions that were derived from N‐arylmethyl thioamides to imines and aziridines were carried out. The reactions of imines gave the addition products of N‐thioacyl‐1,2‐diamines in a highly diastereoselective manner in good‐to‐excellent yields. The diastereomeric purity of these N‐thioacyl‐1,2‐diamines could be enriched by simple recrystallization. The reduction of N‐thioacyl‐1,2‐diamines with LiAlH₄ gave their corresponding 1,2‐diamines in moderate‐to‐good yields with retention of their stereochemistry. The oxidative‐desulfurization/cyclization of an N‐thioacyl‐1,2‐diamine in CuCl₂/O₂ and I₂/pyridine systems gave the cyclized product in moderate yield and the trans isomer was obtained as the sole product. On the other hand, a similar cyclization reaction with antiformin (aq. NaClO) as an oxidant gave the cis isomer as the major product. The reactions of N‐tosylaziridines gave the addition products of N‐thioacyl‐1,3‐diamines with low diastereoselectivity but high regioselectivity and in good‐to‐excellent yields. The use of AlMe₃ as an additive improved the efficiency and regioselectivity of the reaction. The stereochemistry of the obtained products was determined by X‐ray diffraction.     

Copper-mediated cyanation reactions

Aryl nitriles can be efficiently synthesized through transition-metal-mediated cyanation of aryl halides, arenes, aryl boronic acids, and so on. Among those most commonly used transition-metals, copper catalysts are surely much more inexpensive and easier to handle, compared to any other metal catalysts. Considering the high-efficiency of copper catalysts in the activation of C–X, C–H, and C–B bond as well as in the formation of C–CN bond, this Letter summarizes various copper-mediated cyanations based on the different kinds of cyanide reagents, such as metal cyanides, potassium hexacyanoferrate(II), acetone cyanohydrins, DDQ, AIBN, benzyl cyanide, malononitrile, nitromethane, and DMF. Our group’s recent contributions to this area are also demonstrated.     

Ligand free open air copper(II) mediated aryl formamidation and amination of aryl halides

A simple synthetic procedure for direct formamidation and amination of aryl halides mediated by copper(II) salts was developed in open air, without an external ligand in formamide with potassium carbonate as a base. This approach is particularly efficient when electron active aryl halides are used as substrates. In these cases almost quantitative formamidation was observed.     

An improved palladium(II)-catalyzed method for the synthesis of aryl ketones from aryl carboxylic acids and organonitriles

A palladium(II)-catalyzed decarboxylative protocol for the synthesis of aryl ketones has been developed. The addition of TFA was shown to improve the reaction yield and employing THF as solvent enabled the use of solid nitriles and in only a small excess. Using this method, five different benzoic acids reacted with a wide range of nitriles to produce 29 diverse (hetero)aryl ketone derivatives in up to 94% yield.