Lewis base activation of lewis acids. Addition of silyl ketene acetals to aldehydes

The weak Lewis acid silicon tetrachloride can be activated by catalytic amounts of the chiral bisphosphoramide (R,R)-3 to form a highly reactive, chiral trichlorosilyl cation which is an extremely effective promoter of aldol addition reactions between aldehydes and silyl ketene acetals. The tert-butyldimethylsilyl ketene acetal of methyl acetate adds nearly instantaneously to aromatic and olefinic aldehydes as well as aliphatic aldehydes (albeit more slowly) with excellent enantioselectivity. The homologous tert-butyldimethylsilyl ketene acetal of tert-butyl propanoate adds with nearly exclusive anti diastereoselectivity to a similar range of aldehydes also with excellent enantioselectivity. The origin of the slower reaction rate with aliphatic aldehydes is revealed to be the formation of chlorosilyl ether adducts.     

Beiträge zur Chemie der Silicium-Stickstoff-Verbindungen. C. Die partielle Ammonolyse des Siliciumtetrachlorids Hexachlordisilazan. Hexachlorcyclotrisilazan

Partial ammonolysis of silicon tetrachloride in diethylether below ?60°C gives hexachlorodisilazane (I; yield 40%), hexachlorocyclotrisilazane (II; 3–5%) and polychlorosilazanes, mainly [Cl₂SiNH]_x (III). For a survey of the single steps of this reaction, see scheme 2. Cleavage of III with HCl, HBr (in benzene or ether) or SiCl₄ (elevated temperature and pressure) gives more I in moderate and octachlorotrisildiazane (IV) in very low yield. I reacts with butyllithium to lithium-bis(trichlorosilyl)amide (IX). This compound forms deutcrohexachlorodisilazane on reaction with heavy water and decomposes on heating into LiCl and decachloro-bis(silyl)-cyclodisilazane (XIX). Physical properties and analytical data of the conpounds are summarized in tables 2 and 3. Many other reactions of I, II and IX may be seen in chapter 4a, b as well as in schemes 3, 4 and 6.     

Chemistry of silicon-nitrogen compounds. 165. On the crystalline products from the reaction of silicon tetrachloride with nitrogen in a glow discharge. Single crystal X-ray structure determination of N(SiCl3)3 and Cl3SiN(SiCl2)2NSiCl3

Of the two crystalline products obtained by reacting a silicon tetrachloride/nitrogen mixture in a glow discharge tube, the more volatile (m. p. 78°C) has been confirmed to be tris(trichlorosilyl)amine NSi₃Cl₉ whereas the less volatile component (m. p. 66°C) has been identified as N,N′-bis(trichlorosilyl)-Si,Si′-tetrachloro-cyclodisildiazane N₂Si₄Cl₁₀. These conclusions are supported by mass and vibrational spectroscopy and single crystal X-ray structures. NSi₃Cl₉ possesses a nearly planar NSi₃ skeleton with average N? Si distances of 1.734(2) Å. The N₂Si₄ fragment of N₂Si₄Cl₁₀ is roughly planar with endocyclic N? Si? N and Si? N? Si angles of 89.2(1) and 90.8(1)°, respectively, and mean N? Si distances of 1.731(3) (endocyclic) and 1.687(3) Å (exocyclic).     

Lewis base catalyzed, enantioselective aldol addition of methyl trichlorosilyl ketene acetal to ketones

The catalytic enantioselective addition of an acetate enolate equivalent to ketones is described. Methyl trichlorosilyl ketene acetal reacts with a wide range of ketones in the presence of pyridine N-oxide to afford the aldol addition products in excellent yields. Chiral 2,2'-pyridyl bis-N-oxides bearing various substituents at the 3,3'- and 6,6'-positions also provide excellent yields of the aldol products with variable enantioselectivities ranging from 94/6 er for aromatic ketones to nearly racemic for aliphatic ketones. An X-ray crystal structure of the complex between a catalyst and silicon tetrachloride (((P)-(R,R)-19.SiCl(4))) has been obtained. Extensive computational analysis provides a stereochemical rationale for the observed trends in enantioselectivities.     

Synthesis and characterization of branched polystyrene. Part I. Synthesis of four- and six-branch star polystyrene

The synthesis of very well defined four- and six-branched polystyrene has been carried out. Anionic polymerization initiated by butyllithium in benzene–tetrahydrofuran medium gave single chains of narrow distribution. Coupling this living polystyryllithium with bis(trichlorosilyl)ethane gave a maximum of four branches. Coupling with the cyclic trimer of phosphonitrilic chloride gave a maximum of six branches. The reaction procedures have been discussed and mechanisms suggested for some of the reactions.     

Catalytic, enantioselective aldol additions to ketones

Catalytic, enantioselective additions of a trichlorosilyl ketene acetal to ketones have been demonstrated. The trichlorosilyl enolate of methyl acetate undergoes a rapid and high-yielding aldol addition to a wide range of ketones (aromatic, olefinic, acetylenic, aliphatic) in the presence of a catalytic amount of pyridine N-oxide. Moreover, in the presence of a catalytic amount (10 mol %) of a chiral bispyridine bis N-oxide (possessing both axial and central chiral elements) the aldol addition takes place again in excellent yield and with good stereoselectivity. The enantioselectivities of the additions are highly variable (7-86% ee) and are strongly dependent on the structure of the ketone acceptor. Aromatic methyl ketones gave the highest selectivity, whereas olefinic ketones were the least selective.     

Asymmetric Catalysis with Silicon‐Based Cuprates: Enantio‐ and Regioselective Allylic Substitution of Linear Precursors

An enantio‐ and regioselective allylic silylation of linear allylic phosphates that makes use of catalytically generated cuprate‐type silicon nucleophiles is reported. The method relies on soft bis(triorganosilyl) zincs as silicon pronucleophiles that are prepared in situ from the corresponding hard lithium reagents by transmetalation with ZnCl₂. With a preformed chiral N‐heterocyclic carbene–copper(I) complex as catalyst, exceedingly high enantiomeric excesses are achieved. The new method is superior to existing ones using a silicon–boron reagent as the source of the silicon nucleophile.     

Effect of frequency on the deposition of microcrystalline silicon from tetrachlorosilane in low-pressure r.f. plasmas

The efficiency of reduction of silicon tetrachloride and the rate of deposition of Si in a low-pressure r.f. plasma was investigated at two frequencies (0.4 and 27 MHz) as a function of position with regard to the rf coil, pressure, and time of deposition. At 27 MHz the decomposition efficiency of silicon tetrachloride and the deposition rate of Si are about three times higher than at 0.4 MHz.     

A Disilene Base Adduct with a Dative Si–Si Single Bond

An experimental and theoretical study of the base‐stabilized disilene 1 is reported, which forms at low temperatures in the disproportionation reaction of Si₂Cl₆ or neo‐Si₅Cl₁₂ with equimolar amounts of NMe₂Et. Single‐crystal X‐ray diffraction and quantum‐chemical bonding analysis disclose an unprecedented structure in silicon chemistry featuring a dative Si→Si single bond between two silylene moieties, Me₂EtN→SiCl₂→Si(SiCl₃)₂. The central ambiphilic SiCl₂ group is linked by dative bonds to the amine donor and the bis(trichlorosilyl)silylene acceptor, which leads to push–pull stabilization. Based on experimental and theoretical examinations a formation mechanism is presented that involves an autocatalytic reaction of the intermediately formed anion Si(SiCl₃)₃^? with neo‐Si₅Cl₁₂ to yield 1 .     

Chiral phosphine oxide BINAPO as a Lewis base catalyst for asymmetric allylation and aldol reaction of trichlorosilyl compounds

Chiral phosphine oxide BINAPO, which was readily prepared from chiral phosphine BINAP, exhibited good catalytic activities in the reaction of trichlorosilyl compounds via hypervalent silicate intermediates. The allylation of aldehydes with allyltrichlorosilanes in the presence of a catalytic amount of BINAPO gave the allylated adducts in good enantioselectivities (up to 79% ee) wherein a combination of diisopropylethylamine and tetrabutylammonium iodide as additives was crucial to accelerate the catalytic cycle. ³¹P NMR analysis of the phosphine oxide suggested that the amine promoted the dissociation of phosphine oxide from silicon atom. BINAPO also promoted the enantioselective aldol reaction of aldehydes with trichlorosilyl enol ethers in the presence of diisopropylethylamine as an additive to afford the corresponding aldol adducts in high diastereo- and enantioselectivities (up to syn/anti=1/25, 96% ee (anti)).     

Beiträge zur Chemie der Silicium-Stickstoff-Verbindungen. CV. Ringschlußreaktionen mit 1,5-Bis(alkylamino)trisildioxanen

1.5-Bis(methylamino)hexamethyltrisildioxane reacts in the presence of triethylamine easily with germanium tetrachloride (equ. 1) and ethyldichlorophosphine (equ.2) to give the formerly unknown inorganic eightmembered ring systems Si₃GeN₂O₂ and Si₃PN₂O₂. Respectively. By analogous reacting of silicon tetrachloride only open chained Cl₃Si? Nme? Sime₂? O? Sime₂? O? Sime? NHme (IV; equ. 3) is formed. With metallated 1.5-bis(alkylamino)trisildioxanes, dischlorodiorganylsilanes do not give the expected asymmetric-, but the symmetric cyclotetrasildioxdiazanes V–VII. Dichlorophenylborane, in an analogous reaction, leads to the novel eightmembered ring system BSi₃N₂O₂, but the exact position of the N and O atoms in the ring could not be fixed beyond any doubt. The novel sixmembered ring system BSi₂Ni₂O was realized in compound IX via equ. (6).     

Silicon‐ and Tin‐Based Cuprates: Now Catalytic in Copper!

Silicon‐ and tin‐containing molecules are versatile building blocks in organic synthesis. A stalwart method for their preparation relies on the stoichiometric use of silicon‐ and tin‐based cuprates, although a few copper(I)‐catalyzed or even copper‐free protocols have been known for decades. In this Concept, we describe our efforts towards copper(I)‐catalyzed carbon? silicon and also carbon? tin bond formations using soft bis(triorganosilyl) and bis(triorganostannyl) zinc reagents as powerful sources of nucleophilic silicon and tin. Conjugate addition, allylic substitution, and carbon? carbon multiple bond functionalization is now catalytic in copper!     

Chemistry of 2,5-bis(trimethylsiloxy)furans. III: Synthesis of γ-hydroxybutenolides

γ-Hydrobutenolides were obtained from the reaction of substituted 2,5- bis(trimethylsiloxy)furans with aldehydes and ketones using titanium tetrachloride activation. Similarly, α,β-unsaturated carbonyl compounds reacted as a Michael receptor with the title compounds to give γ-hydroxybutenolides.     

Absorption of polymers at the solution–solid interface. XII. Stabilization of dispersed silica by absorbed styrene–methyl methacrylate copolymers

The ability of styrene–methyl methacrylate copolymers to stabilize silica dispersions has been investigated. Random, block, and graft copolymers covering the entire composition range have been employed in carbon tetrachloride, trichloroethylene, and benzene solutions. Equilibrium sediment volumes and dispersion turbidities provide adequate and concordant estimates of stabilization efficiency. Polystyrene is not adsorbed by precipitated silica from trichloroethylene or benzene and does not stabilize dispersions in these liquids; although adsorbed from carbon tetrachloride, there is no stabilization. Poly(methyl methacrylate) is an efficient dispersion stabilizer, and its performance is independent of molecular weight over a wide range. Random copolymers having styrene contents in excess of ca. 60% do not stabilize in trichloroethylene but do so in carbon tetrachloride, although well adsorbed in both cases. With this major exception, and that of a low-styrene graft copolymer in carbon tetrachloride, copolymers of all structures and compositions stabilize well, better than poly(methyl methacrylate) in the solvents examined. A substantial degree of surface coverage is necessary for optimum stabilization. Subsidiary solution adsorption and layer thickness measurements are also reported.     

Apparatur zur Molekulargewichtsbestimmung an hochverdünnten (10−4M). Lösungen mittels Dampfdruckosmometrie

A vapour pressure osmometer for the determination of number-average molecular weights is described. With this improved design 10^?4M solutions can be measured with a standard deviation of 1.3% (carbon tetrachloride, 30°C). Molecular weight determinations up to 160000 (± 7.5%; polystyrene in carbon tetrachloride) are presented.     

Photochemistry of electron donor-acceptor complexes of the bis(fulvalene) dicobalt mono- and dications

Addition of carbon tetrachloride or chloroform to acetonitrile solutions of the bis(fulvalene)dicobalt monocation results in the appearance of new absorption features which are attributed to formation of electron donor-acceptor complexes. The association constants of these complexes aer 2.36 /mole fraction (carbon tetrachloride) and 2.74 /mole fraction (chloroform). Excitation in the absorption bands of the donor-acceptor complexes results in oxidation of the monocation to the dication with high quantum yields. A donor-acceptor complex is also formed when sodium tetraphenylborate is added to acetonitrile solutions of the bis(fulvalene)dicobalt dication. Spectroscopic determination of the association constant of the dication with tetraphenylborate yields a value of 26.3 /mole fraction. Excitation of the absorption bands of the ion-pair results in high quantum yields for formation of the bis(fulvalene) dicobalt monocation. Biphenyl is found in photolyzed solutions as a byproduct of the oxidation of the tetraphenylborate anion.     

A Practical and Inexpensive One‐Pot Synthesis of Bis(indenyl)­dimethyltitanium with Aqueous Workup Procedure

A simple, reliable, and reproducible procedure for the multi‐gram synthesis of highly pure bis(indenyl)dimethyltitanium is presented. The procedure relies on a one‐pot conversion of inexpensive indene, methyllithium, and titanium tetrachloride to [Ind₂TiMe₂] and a convenient and quick aqueous workup protocol. Overall, quantities of several grams of [Ind₂TiMe₂] can be synthesized within a few hours. The procedure can also be used for the synthesis of [Cp₂TiMe₂] from cyclopentadiene, methyllithium, and titanium tetrachloride.     

Chlorination of secondary phosphine chalcogenides with carbon tetrachloride in the absence of bases

The interaction of bis(2-phenylethyl)phosphine sulfide, bis(2-phenylethyl)phosphine selenide and bis[2-(2-phenyl)propyl]phosphine selenide with carbon tetrachloride under heating (80°C, 8–20 h) leads to the formation of the corresponding chlorophosphine chalcogenides with the yield of 80–90%.

     

Diolato‐silicat‐ und ‐germanat‐Ionen aus wäßrig‐alkalischer Lösung

Polyol Metal Complexes. 35 [1] Diolato Silicate and Germanate Ions from Aqueous Solution Hydrated lithium salts of monoanionic bis(diolato)‐hydroxo complexes of silicon and germanium have been crystallized from alkaline aqueous solutions. The isotypic compounds Li[E(AnErytH_–2)₂(OH)] · H₂O, E = Si ( 1 ) or Ge ( 2 ), AnErytH_–2 = anhydroerythritol dianions, were obtained in the form of pseudomeroedric twins, a fact that may be traced back to orthorhombic pseudosymmetry of the monoclinic crystals. With potassium as the counterion, anhydrous crystals of K[Si(AnErytH_–2)₂(OH)] were grown by evaporating the solvent almost entirely from the aqueous mother liquors.     

Porous Silica Particles Prepared from Silicon Tetrachloride Using Ultrasonic Spray Method

Silica particles having the median diameter of 1 to 3 μm were prepared from silicon tetrachloride vapor by a reaction with water droplets using the ultrasonic spray method. The particle sizes of silicas were controlled by changing the composition of silicon tetrachloride and water. These silica particles had microporous structures from nitrogen and water adsorption measurements. The microporous and mesoporous particles were prepared from the reaction of water droplets including sodium and potassium carbonates with silicon tetrachloride vapor. Copyright 1999 Academic Press.