Enantioselective Synthesis of Silicon-Stereogenic Monohydrosilanes by Rhodium-Catalyzed Intramolecular Hydrosilylation

Enantiopure monohydrosilanes are versatile chiral reagents for alcohol resolution and mechanistic investigation. Herein, we have demonstrated the asymmetric synthesis of monohydrosilanes via an intramolecular hydrosilylation strategy. This protocol is suitable for the synthesis of five- and six-membered cyclic monohydrosilanes, including a class of chiral oxasilacycles, with excellent diastereo-, regio-, and enantioselectivities. Notably, the catalyst loading could be reduced to 0.1 mol % which makes this one of the most efficient methods to access chiral monohydrosilanes. Mechanistic studies and DFT calculations indicate this Rh-catalyzed intramolecular asymmetric hydrosilylation reaction might proceed via a Chalk–Harrod mechanism, and the enantio-determining step was predicted to be oxidative addition of Si?H bond.     

Reduction of carbonyl compounds via hydrosilylation : I. Hydrosilylation of carbonyl compounds catalyzed by tris(triphenylphosphine)chlororhodium

The hydrosilylation of various carbonyl compounds such as simple aldehydes, simple ketones, α,β-unsaturated carbonyl compounds, α-diketones, acyl cyanides and ketones having an electron-withdrawing group on the α-carbon using tris(triphenylphosphine)chlororhodium as a catalyst is described. Solvolysis of these silyl ethers and silyl enol ethers afforded the corresponding reduced products. The hydrosilylation of α,β-unsaturated carbonyl compounds was found to proceed by 1,4-addition. An oxidative adduct of triethylsilane to the rhodium-(I) complex was obtained as a reaction intermediate. The structure of the adduct was discussed on the basis of its IR and far-IR spectra.     

Copper(II) triflate-catalyzed reduction of carboxylic acids to alcohols and reductive etherification of carbonyl compounds

A protocol is described for the reduction of carboxylic acids to primary alcohols using 1,1,3,3-tetramethyldisiloxane (TMDS) and a catalytic amount of Cu(OTf)₂. Aliphatic as well as aromatic carboxylic acids are reduced in high selectivity and good yields. TMDS/Cu(OTf)₂ has also been found to be an efficient catalytic reducing system for the preparation of symmetrical ethers from carbonyl compounds under mild conditions.     

Analysis of an unprecedented mechanism for the catalytic hydrosilylation of carbonyl compounds

This work details an in-depth evaluation of an unprecedented mechanism for the hydrosilylation of carbonyl compounds catalyzed by (PPh3)2Re(O)2I. The proposed mechanism involves addition of a silane Si-H bond across one of the rhenium-oxo bonds to form siloxyrhenium hydride intermediate 2 that reacts with a carbonyl substrate to generate siloxyrhenium alkoxide 4, which, in turn, affords the silyl ether product. Compelling evidence for the operation of this pathway includes the following: (a) isolation and structural characterization by X-ray diffraction of siloxyrhenium hydride intermediate 2, (b) demonstration of the catalytic competence of intermediate 2 in the hydrosilylation reaction, (c) 1H and 31P{1H} NMR and ESI-MS evidence for single-turnover conversion of 2 into 1, (d) observation of intermediate 2 in the working catalyst system, and (e) kinetic analysis of the catalytic hydrosilylation of carbonyl compounds by 1.     

DFT study on mechanism of carbonyl hydrosilylation catalyzed by high-valent molybdenum (IV) hydrides

Density functional theory (DFT) calculations have been employed to investigate hydrosilylation of carbonyl compounds catalyzed by three high-valent molybdenum (VI) hydrides: Mo(NAr)H(Cp)(PMe₃) (1A), Mo(NAr)H(PMe₃)₃ (1B), and Mo(NAr)H (Tp)(PMe₃) (Tp?=?tris(pyrazolyl) borate) (1C). Three independent mechanisms have been explored. The first mechanism is “carbonyl insertion pathway”, in which the carbonyls insert into Mo?H bond to give a metal alkoxide complex. The second mechanism is the “ionic hydrosilylation pathway”, in which the carbonyls nucleophilically attacks η¹-silane molybdenum adduct. The third mechanism is [2 + 2] addition mechanism which was proposed to be favorable for the high-valent di-oxo molybdenum complex MoO₂Cl₂ catalyzing the hydrosilylation. Our studies have identified the “carbonyl insertion pathway” to be the preferable pathway for three molybdenum hydrides catalyzing hydrosilylation of carbonyls. For Mo(NAr)H (Tp)(PMe₃) (Tp?=?tris(pyrazolyl) borate), the proposed nonhydride mechanism experimentally is calculated to be more than 32.6?kcal/mol higher than the “carbonyl insertion pathway”. Our calculation results have derived meaningful mechanistic insights for the high-valent transition metal complexes catalyzing the reduction reaction.     

Borane‐Catalyzed Reductive α‐Silylation of Conjugated Esters and Amides Leaving Carbonyl Groups Intact

Described herein is the development of the B(C₆F₅)₃‐catalyzed hydrosilylation of α,β‐unsaturated esters and amides to afford synthetically valuable α‐silyl carbonyl products. The α‐silylation occurs chemoselectively, thus leaving the labile carbonyl groups intact. The reaction features a broad scope of both acyclic and cyclic substrates, and the synthetic utility of the obtained α‐silyl carbonyl products is also demonstrated. Mechanistic studies revealed two operative steps: fast 1,4‐hydrosilylation of conjugated carbonyls and then slow silyl group migration of a silyl ether intermediate.     

Polybutylene terephthalate reactive blending with polymethylhydrosiloxane by ruthenium‐catalyzed carbonyl hydrosilylation reaction

Carbonyl hydrosilylation reaction was developed to prepare reactive blending between PBT and polymethylhydrosiloxane (PMHS). It focused on the addition reaction of Si–H groups from PMHS onto carbonyl groups from PBT catalyzed by triruthenium dodecacarbonyl (Ru₃(CO)₁₂). An approach on PBT model compounds was carried out and investigated by NMR spectroscopy to evidence the potentiality and efficiency of carbonyl hydrosilylation reaction. At temperatures up to 100 °C, the hydrosilylation reaction can reach 33 mol% conversion in a few hours. Side reactions were also highlighted. Such side reactions can reach more than 23 mol% of the final products when temperature increases to 180 °C. Then hydrosilylation reaction was extended to PBT modification with a molar ratio of ester group/SiH = 3.5 and viscosity ratio polysiloxane/PBT = 4.0 × 10^?5. The reaction was carried out in an internal mixer at 220 °C and followed through the evolution of the torque of the reactional medium. Samples for different processing times were investigated by SEM and rheology. From these analyses, the dispersion of PMHS was promoted with diameters of few micrometers. The elastic behavior of final material was characteristic of solid or gel‐like structures, suggesting a network structure formation consistent with the gel fraction increase from 0 to 0.55. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 1855–1868     

Reagents and synthetic methods 52. Silane reduction of carbonyl compounds in the presence of iodine

Synthetic utility of 1,1,3,3-tetramethyldisiloxane (TMDS) reagent under the influence of iodine is described. TMDS reagent in combination with iodine produces alkyl iodides from carbonyl compounds and oxiranes in good to excellent yields. Reduction of quinones into hydroquinones is also described. The mentioned transformations are explained from mechanistic points of view.     

Chemoselective Synthesis of Substituted Imines,Secondary Amines,and β‐Amino Carbonyl Compounds from Nitroaromatics through Cascade Reactions on Gold Catalysts

Substituted imines, α,β‐unsaturated imines, substituted secondary amines, and β‐amino carbonyl compounds have been synthesized by means of new cascade reactions with mono‐ or bifunctional gold‐based solid catalysts under mild reaction conditions. The related synthetic route involves the hydrogenation of a nitroaromatic compound in the presence of a second reactant such as an aldehyde, α,β‐unsaturated carbonyl compound, or alkyne, which circumvents an ex situ reduction process for producing the aromatic amine. The process is shown to be highly selective towards other competing groups, such as double bonds, carbonyls, halogens, nitriles, or cinnamates, and thereby allows the synthesis of different substituted nitrogenated compounds. For the preparation of imines, substituted anilines are formed and condensed in situ with aldehydes to provide the final product through two tandem reactions. High chemoselectivity is observed, for instance, when double bonds or halides are present within the reactants. In addition, we show that the Au/TiO₂ system is also able to catalyze the chemoselective hydrogenation of imines, so that secondary amines can be prepared directly through a three‐step cascade reaction by starting from nitroaromatic compounds and aldehydes. On the other hand, Au/TiO₂ can also be used as a bifunctional catalyst to obtain substituted β‐amino carbonyl compounds from nitroaromatics and α,β‐unsaturated carbonyl compounds. Whereas gold sites promote the in situ formation of anilines, the intrinsic acidity of Ti species on the support surface accelerates the subsequent Michael addition. Finally, two gold‐catalyzed reactions, that is, the hydrogenation of nitro groups and a hydroamination, have been coupled to synthesize additional substituted imines from nitroaromatic compounds and alkynes.     

Propargylsilanes as Reagents for Synergistic Gold(I)‐Catalyzed Propargylation of Carbonyl Compounds: Isolation and Characterization of σ‐Gold(I) Allenyl Intermediates

Reported herein is the isolation and characterization, for the first time, of a σ‐gold allenyl complex as an intermediate in gold catalysis. This intermediate was captured during the study of a novel gold(I)‐catalyzed propargylation of carbonyl compounds with propargylsilanes. Notably, the gold‐catalyzed propargylation reaction, which proceeds with aldehydes and ketones, can be driven to the formation of either homopropargyl silyl ethers or the in situ synthesis of corresponding 2‐silyl‐4,5‐dihydrofurans.     

有机锡二聚体对醛的选择性催化

以Bu2SnO与CF3SO3H(TfOH)直接反应合成了有机锡二聚体[Bu2Sn(OH)(OTf)(H2O)]2, 以[Bu2Sn(OH)(OTf)(H2O)]2为催化剂考察了醛的硅氢化反应. 与传统的路易斯酸催化剂相比, 有机锡二聚体催化剂不仅具有合成简单、贮存容易、使用方便、易于分离、用量少和催化效率高等优点, 而且对醛基的还原催化具有很高的选择性, 且不受分子内和反应体系中其它羰基化合物或可还原基团的影响.     

Computational study on the reaction mechanism of hydrosilylation of carbonyls catalyzed by high-valent rhenium(V)-di-oxo complexes

Density functional theory (DFT) calculations have been performed to elucidate the reaction mechanism of hydrosilylation of carbonyl compounds catalyzed by high-valent rhenium(V)-di-oxo complexes ReO2I(PR3)2 (R = Me, Ph). The calculations suggest that the most favorable mechanism involves the rate-determining dissociative [2 + 2] addition of the Si-H bond across a Re=O bond to form a Re(V) hydrido siloxy intermediate; this is followed by carbonyl coordination, reduction of the carbonyl, rearrangement, and final intramolecular nucleophilic attack from the alkoxy group to the silyl center (dissociative retro-[2 + 2] addition). It was also found that the additional oxo ligand in the ReO2I(PR3)2 complexes promotes the [2 + 2] addition across the rhenium-oxo bond both kinetically and thermodynamically, as compared to the neutral rhenium(V)-mono-oxo complex ReOCl3(PMe3)2. The effect of different silanes on the [2 + 2] addition barriers is also studied.     

Mechanistic investigation on hydrogenation and hydrosilylation of ethylene catalyzed by rhenium nitrosyl complex

The mechanistic study for hydrogenation and hydrosilylation of ethylene catalyzed by a rhenium nitrosyl complex is carried out with the aid of density functional theory computations. The hydrogenation of ethylene is found to be available kinetically in which the oxidative addition of H₂ plays a role in decreasing the reaction barrier. For the case of hydrosilylation of ethylene, it is found the oxidative addition of HSiMe₃ cannot occur due to steric reasons, instead, a σ-bond metathesis process for reductive elimination of C₂H₅SiMe₃ is proposed. The major reason for the inaccessibility for the hydrosilylation is resulted from the fact that the oxidative addition of HSiMe₃ cannot give a more stable intermediate.     

Synthesis and optical properties of σ–π conjugated organic–inorganic hybrid gels

Organic–inorganic hybrid gels containing Si‐vinylene units have been synthesized by a hydrosilylation reaction of tri‐ or tetra‐ethynyl aryl compounds, 1,3,5‐triethynylbenzene (TEB), 3,3′,5,5′‐tetraethynylbiphenyl (TEBP), or tetrakis(4‐ethynylphenyl)methane (TEPM), and bisdimethylsilyl compounds, 1,1,3,3‐tetramethyldisiloxane (TMDS) or 1,4‐bisdimetylsilylbenzene (BDMSB), in toluene. Network structure of the resulting gels was quantitatively characterized by a scanning microscopic light scattering. The reactions yielded the gels having homogeneous network structure of 1.5–2.9 nm mesh size under the monomer concentrations that were relatively higher than the critical gelation concentration. The gels obtained from TEB showed broad absorption in the range from 340 to 370 nm, and emission in the range from 440 to 490 nm. The TEB–BDMSB gels showed remarkable red shift of the emission in comparison with that of the corresponding reaction solutions derived from the network formed by σ–π conjugation. The TEPM–TMDS, BDMSB gels exited by 280 nm showed not only the emission peak at around 360 nm derived from TEPM, but the broad peak at around 420 nm, which should be derived from interaction between phenyl groups of TEPM in the gels. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1360–1368     

Kinetics and mechanism of the formation of poly[(1,1,3,3-tetramethyldisiloxanyl)ethylene] and poly(methyldecylsiloxane) by hydrosilylation

The kinetics of the formation of poly(carbosiloxane), as well as of alkyl-substituted poly(siloxane), by Karstedt's catalyst catalyzed hydrosilylation were investigated. Linear poly(carbosiloxane), poly[(1,1,3,3-tetramethyldisiloxanyl)ethylene], (PTMDSE), was obtained by hydrosilylation of 1,3-divinyltetramethyldisiloxane (DVTMDS) and 1,1,3,3-tetramethyldisiloxane (TMDS), while alkyl-substituted poly(siloxane), poly(methyldecylsiloxane), (PMDS), was synthesized by hydrosilylation of poly(methylhydrosiloxane) (PMHS) and 1-decene. To investigate the kinetics of PTMDSE formation, two series of experiments were performed at reaction temperatures ranging from 25 to 56 °C and with catalyst concentrations ranging from 7.0 × 10⁻⁶ to 3.1 × 10⁻⁵ mol Pt/mol CHCH₂. A series of experiments was performed at reaction temperatures ranging from 28 to 48 °C, with catalyst concentrations of 7.0 ×10⁻⁶ mol of Pt per mol of CHCH₂, when kinetics of PMDS formation was investigated. All reactions were carried out in bulk, with equimolar amounts of the reacting Si H and CHCH₂ groups. The course of the reactions was monitored by following the disappearance of the Si H bands using quantitative infrared spectroscopy. The results obtained showed typical first order kinetics for the PTMDSE formation, consistent with the proposed reaction mechanism. In the case of PMDS an induction period occurred at lower reaction temperatures, but disappeared at 44 °C and the rate of Si H conversion also started to follow the first-order kinetics. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2246–2258, 2007     

Hydrosilylation of carbonyl compounds using a PhSeSiMe(3)/Bu(3)SnH/AIBN system

[reaction: see text] When carbonyl compounds were allowed to react with phenyl trimethylsilyl selenide and tributylstannyl hydride in the presence of a catalytic amount of AIBN as a radical initiator, the hydrosilylation of the carbonyl compounds efficiently proceeded to give the corresponding silyl ethers in moderate to good yields.     

Reaction of carbonyl compounds with trialkylsilyl phenylselenide and tributylstannyl hydride under radical conditions

A novel method for the hydrosilylation of carbonyl compounds has been developed. When carbonyl compounds were allowed to react with trimethylsilyl phenylselenide and tributylstannyl hydride in the presence of a catalytic amount of AIBN as the radical initiator, hydrosilylation of the carbonyl compounds efficiently proceeded to give the corresponding silyl ethers in moderate to good yields. In the absence of carbonyl compounds, the triethylsilyl hydride was obtained by the reaction of PhSeSiEt(3) with Bu(3)SnH. Although the tributylgermyl phenylselenide instead of PhSeSiMe(3) was treated with tributylstannyl hydride in the presence of a benzaldehyde under radical conditions, hydrogermylated product was not obtained and tributylgermyl hydride was mainly formed.     

Unusual Structure,Fluxionality, and Reaction Mechanism of Carbonyl Hydrosilylation by Silyl Hydride Complex [(ArN)Mo(H)(SiH2Ph)(PMe3)3]

The reactions of bis(borohydride) complexes [(RN?)Mo(BH₄)₂(PMe₃)₂] ( 4 : R=2,6‐Me₂C₆H₃; 5 : R=2,6‐iPr₂C₆H₃) with hydrosilanes afford new silyl hydride derivatives [(RN?)Mo(H)(SiR′₃)(PMe₃)₃] ( 3 : R=Ar, R′₃=H₂Ph; 8 : R=Ar′, R′₃=H₂Ph; 9 : R=Ar, R′₃=(OEt)₃; 10 : R=Ar, R′₃=HMePh). These compounds can also be conveniently prepared by reacting [(RN?)Mo(H)(Cl)(PMe₃)₃] with one equivalent of LiBH₄ in the presence of a silane. Complex 3 undergoes intramolecular and intermolecular phosphine exchange, as well as exchange between the silyl ligand and the free silane. Kinetic and DFT studies show that the intermolecular phosphine exchange occurs through the predissociation of a PMe₃ group, which, surprisingly, is facilitated by the silane. The intramolecular exchange proceeds through a new non‐Bailar‐twist pathway. The silyl/silane exchange proceeds through an unusual Mo^VI intermediate, [(ArN?)Mo(H)₂(SiH₂Ph)₂(PMe₃)₂] ( 19 ). Complex 3 was found to be the catalyst of a variety of hydrosilylation reactions of carbonyl compounds (aldehydes and ketones) and nitriles, as well as of silane alcoholysis. Stoichiometric mechanistic studies of the hydrosilylation of acetone, supported by DFT calculations, suggest the operation of an unexpected mechanism, in that the silyl ligand of compound 3 plays an unusual role as a spectator ligand. The addition of acetone to compound 3 leads to the formation of [trans‐(ArN)Mo(OiPr)(SiH₂Ph)(PMe₃)₂] ( 18 ). This latter species does not undergo the elimination of a Si? O group (which corresponds to the conventional Ojima′s mechanism of hydrosilylation). Rather, complex 18 undergoes unusual reversible β‐CH activation of the isopropoxy ligand. In the hydrosilylation of benzaldehyde, the reaction proceeds through the formation of a new intermediate bis(benzaldehyde) adduct, [(ArN?)Mo(η²‐PhC(O)H)₂(PMe₃)], which reacts further with hydrosilane through a η¹‐silane complex, as studied by DFT calculations.     

Determination of carbonyl compounds in exhaust gas by using a modified DNPH-method

The determination of carbonyl compounds in gaseous samples is usually accomplished by enrichment methods, in which 2,4-dinitrophenyl-hydrazine (DNPH) as a derivatization reagent has become established to a large extent. However, the conventional methods of DNPH-impingers and of DNPH-cartridges are applicable to emission measurements in a limited way only, depending on the NO₂-concentration in the exhaust gas. It could be proved that DNPH-derivatives, as well as DNPH, are also decomposed by NO₂ at a different speed, in which the hydrazones of unsaturated carbonyl compounds are probably more sensitive than those of the saturated carbonyl compounds. In view of this fact, the collecting methods had to be modified to avoid losses with the enrichment. The analysis of the compounds is carried out by HPLC with an effective gradient-system which is able to separate and detect the carbonyl compounds in exhaust gas within 16 min. Furthermore, a simple working-up procedure is presented which facilitates a parallel analysis by GC.     

Direct synthesis of tetrahydropyrans via one-pot Babier-Prins cyclization of allylbromide with carbonyl compounds promoted by RTILs BPyX/SnX′2 or BBIMBr/SnBr2

Tetrahydropyran compounds can be directly synthesized from allylbromide and carbonyl compounds by means of one-pot Babier-Prins cyclization promoted by BPyX/SnX′₂ or BBIMBr/SnBr₂ complex (functionalized RTILs) under solvent-free conditions. 2,6-Homo-bissubstituted- and 2,6,6-trisubstituted, especially 6-(spirocycloalkyl)-, tetrahydropyran compounds can be prepared in good yields.