5-chloro-3,7-dimethyl-5-

This simple procedure resulted in 2H-azirines exclusively in high yields and with retention of chirality at C-2 [24]. Mechanistically, this oxidative synthesis of azirines can be rationalized by invoking the intermediacy of chloro-dimethyl-sulfonium chloride (Me2SCl+- Cl ), which then reacts with the aziridine as indicated in Scheme 12. 

Chloroacetoaldehyde dimethyl acetal Acetaldehyde, chloro-, dimethyl acetal (8) Ethane, 2-chloro-1,1-dimethoxy- (9) (97-97-2)... 

Propanol, titanium (4+) salt, 65, 230 2-Propanone, l-bromo-3-chloro-, dimethyl acetal, 65, 32 Propargyl bromide (106-96-7), 66, 77, 79, 86... 

The reaction of an w-alkyl(chloro)(dimethyl)silane or w-trialkylchlorosilane of the type RMe2SiX or R3SiX (X = Cl) with a hydrothermally activated silica represents the second and more popular approach. Excellent mass transfer characteristics with peptides can be... 

A. CHLORO(DIMETHYL HYDROGEN PHOSPHITE-P) (DIMETHYL PHOSPHITO-/ ) (TRIPHENYLPHOSPHINE) PLATINUM(II)... 

The enantiomerically pure l-[(benzyl(dimethyl)silyl)methyl]pyrrolidine, obtained from ben-zyl(chloro)(dimethyl)silane and (5,)-2-(methoxymethyl)pyrrolidine , afforded after deprotonation and subsequent alkylation the diastereomerically pure (by NMR spectroscopy) (a-alkylben-zyl)silanes2. To obtain this high degree of diastereoselectivity, the alkylation had to be performed in the weakly complexing solvent diethyl ether. In THF a diastereomeric ratio of only 3 1 was found with iodomethane as alkylating agent. 

Combinations of metal halides (e. g. FeCl3, A1C13) with compounds containing an active halogen atom (e. g. a-chloro-dimethyl ether, benzyl chloride, 2,3-dichloro THF). 

A. CHLORO[DIMETHYL PROTOPORPHYRINATO(2-)]IRON(III), Chloro [ dimethyl 7,12-DiethenyI-3,8,13,17-tetramethyl-21/7,23 //-porphine-2,18-dipropionato- (2- )] iron (III)... 

FeCl(C36H36N404) (iron(III), chloro [dimethyl 7,12-diethenyl-3,8,13,17-te tramethyl-21H, 23//-porphine-2,18-dipropionato(2-)]-), 20 148 FeCl(C3[Pg.291]

Vinylchlorosilanes undergo Friedel-Crafts alkylation with aromatic compounds in the presence of Lewis acids to give 2-(chlorosilyl)ethylarenes [Eq. (17)].lb 32,33 The reactivity of vinylchlorosilanes for the alkylation of aromatic compounds is slightly lower than that of allylchlorosilanes.lb 3,32 The reactivity of vinylsilanes for alkylation depends on the substituents on the silicon of the vinylsilane. The reactivity of vinylchlorosilanes decreases in the following order dichloro(methyl)vinyl-silane > trichlorovinylsilane > chloro(dimethyl)vinylsilane. The alkylation of mono-substituted benzenes such as toluene, chlorobenzene, and biphenyl with di-chloro(methyl)vinylsilane (lc) at 75-80 °C for 2h affords alkylated products in 50-63% yields.32... 

Indoles 371 are selectively acylated at the 3-position to give high yields of compounds 372 on treatment with a wide variety of acyl chlorides in dichloromethane in the presence of chloro(diethyl)aluminium or chloro(dimethyl)-aluminium. The reaction proceeds under mild conditions (at 0 °C or rt, mainly for 1.5 h) and is applicable to indoles bearing various functional groups (both acid and base sensitive indoles) without NH protection (Equation 84) <20000L1485>. 

Telluran(VI) Chloro-dimethyl-triiodo- E12b, 567 (Chloriod-Add.)... 

C10H22O 5-methyl-2-isopropyl-1-hexanol 2051-33-4 486.15 48.543 1.2 21399 ClOH23CISi chloro(dimethyl)octylsilane 18162-84-0 496.60 43.558 1,2... 

Wrackmeyer etal. described how (Z)-2-chloro-(dimethyl)stannyl-3-diethylborylpent-2-ene 44, obtained by reacting chlorodimethyl(prop-l-ynyl)stannane with triethylborane, isomerizes into (Z)-3-chloro-(dimethyl)stannyl-2-diethyl-borylpent-2-ene 45 when treated in THE with powdered sodium amide at 65 °C (Scheme 3) <2002ZN1251>. Pure 3,5-diethyl-l,l,2,4-tetramethyl-2,3-dihydro-l//-l,3-stannaborole 29a was obtained by the reaction of 45 in hexane with a suspension of lithium diisopropylamide (LDA) in toluene at —78°C. The reaction goes to completion by allowing the reaction mixture to reach room temperature and then by briefly heating to reflux. The yields of compounds 45 and 29a were 78% and 93%, respectively. 

Recently, Wrackmeyer /. synthesized 2,3-dihydro-l//-l,3-stannaborole 29b by treating ( )-2-chloro(dimethyl)-stannyl-3-diethylboryl-A, A -dimethyl-2-pentenylamine 48 with LDA in THF (Equation 5) <2003JOM188>. The cyclization owes its success to the high basicity of LDA that abstracts a proton from one of the ethyl groups at boron the resulting carbanion acts as a nucleophile attacking the tin atom. Diisopropylamine and lithium chloride are eliminated from the reaction. 

A solution of compound 182 (55.3 mg, 0.13 mmol) [Eq. (13)], (bromomethyl)chloro dimethyl silane (23 p,L, 0.17 mmol), and triethylamine (35 p,L, 0.26 mmol) in 1 mL of dry CH Clj was stirred for 3 h at room temperature, and then the solvent was evaporated under reduced pressure. The residue was rapidly eluted from a column of basic silica gel (hexane-EtOAc, 3 1) to afford an unstable syrup. This silyl ether was dissolved under argon in 2 mL of dry degased benzene. This solution was heated under reflux, and a solution of tributyltin hydride (56 mg, 0.2 mmol) and AIBN (2%) in 1 mL of benzene was added dropwise over 1 h. The heating was continued for 3 h, and benzene was evaporated. Methanol (0.2 mL), THE (0.2 mL), 30% HjOj (0.3 mL), and NajCOj (16 mg) were added to the residue. The mixture was refluxed for 4 h. Evaporation and column chromatography (hexanes-EtOAc, 1 1) gave the diol 60 (40 mg, 71%) as a gum [a]j, —12° (c 1, CHCI3). 

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