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Product formation, steric hindrance

The most frequently used organocuprates are those m which the alkyl group is pri mary Steric hindrance makes secondary and tertiary dialkylcuprates less reactive and they tend to decompose before they react with the alkyl halide The reaction of cuprate reagents with alkyl halides follows the usual 8 2 order CH3 > primary > secondary > tertiary and I > Br > Cl > F p Toluenesulfonates are somewhat more reactive than halides Because the alkyl halide and dialkylcuprate reagent should both be primary m order to produce satisfactory yields of coupled products the reaction is limited to the formation of RCH2—CH2R and RCH2—CH3 bonds m alkanes... [Pg.603]

In the absence of steric factors e.g. 5 ), the attack is antiparallel (A) (to the adjacent axial bond) and gives the axially substituted chair form (12). In the presence of steric hindrance to attack in the preferred fashion, approach is parallel (P), from the opposite side, and the true kinetic product is the axially substituted boat form (13). This normally undergoes an immediate conformational flip to the equatorial chair form (14) which is isolated as the kinetic product. The effect of such factors is exemplified in the behavior of 3-ketones. Thus, kinetically controlled bromination of 5a-cholestan-3-one (enol acetate) yields the 2a-epimer, (15), which is also the stable form. The presence of a 5a-substituent counteracts the steric effect of the 10-methyl group and results in the formation of the unstable 2l5-(axial)halo ketone... [Pg.274]

The formation of isomeric aldehydes is caused by cobalt organic intermediates, which are formed by the reaction of the olefin with the cobalt carbonyl catalyst. These cobalt organic compounds isomerize rapidly into a mixture of isomer position cobalt organic compounds. The primary cobalt organic compound, carrying a terminal fixed metal atom, is thermodynamically more stable than the isomeric internal secondary cobalt organic compounds. Due to the less steric hindrance of the terminal isomers their further reaction in the catalytic cycle is favored. Therefore in the hydroformylation of an olefin the unbranched aldehyde is the main reaction product, independent of the position of the double bond in the olefinic educt ( contrathermodynamic olefin isomerization) [49]. [Pg.24]

Catalyst 70 is very effective for the reaction of terminal alkenes, however 1,1-disubstituted olefins provide hydrosilylation products presumably, this is due to steric hindrance [45]. When a catalyst with an open geometry (78 or 79) is employed, 1,1-disubstituted alkenes are inserted into C-Y bonds to give quaternary carbon centers with high diastereoselectivities (Scheme 18). As before, initial insertion into the less hindered alkene is followed by cyclic insertion into the more hindered alkene (entry 1) [45]. Catalyst 79 is more active than is 78, operating with shorter reaction times (entries 2 and 3) and reduced temperatures. Transannular cyclization was possible in moderate yield (entry 4), as was formation of spirocyclic or propellane products... [Pg.233]

The alcohols are intermediates in the formation of ketones. Isomerization of the products is not observed. Hydroxylation at the 2-position is favored over that at the 3-position, and the latter is preferred over hydroxylation at the 4-position. Solubility and concentration in the reaction medium, intrazeolite diffusion of the reactants, steric hindrance at the reactive carbon center, and C-H bond strength influence the reactivity and H202 selectivity (Table XXIV). The advantage of the large-pore Ti-beta over TS-1 in the oxidation of bulky alkane molecules is shown by the results in Table XXV. [Pg.107]

In MeOH the hydride reacts with higher a-olefins, propene, 1-hexene and 1-hexadecene with formation of only the linear insertion product, probably for steric reasons. In all the insertion products, the alkyl ligand presents the /f-agoslic interaction. At room temperature, the insertion of ethene is quantitative whereas with propene an appreciable amount of the hydride is present, with 1-hexene the hydride prevails, with 1-hexadecene only the hydride is present. The fact that the position of the insertion equilibrium strongly depends on the chain length of the alkyl substituent is probably connected with the high steric hindrance of the ligand [115]. [Pg.162]

The formation of the syn adducts has been explained by considering that carboxylic acids or BF3 catalyze the formation of the ionic intermediate by stabilizing the methoxy ion. This intermediate can then collapse directly to the cis product. Reactions in methanol give instead mainly the trans-1,2-adduct, the solvent collapse from the back-side being very rapid. Furthermore, the difference in syn selectivity, slightly larger for 1,4- than for 1,2-addition, has been attributed to a smaller steric hindrance for syn methoxy (methanol) attack at C(4) than at C(2). [Pg.570]

When the non-coordinating mesitoate system 156 was treated with lithium di-methylcuprate, formation of the anti-S 2 substitution product 157 was observed. Notably, the exclusive formation of the y-substitution product is the result of severe steric hindrance at the a-position, originating from the adjacent isopropyl group [78]. Conversely, the corresponding carbamate 158 was reported, on treatment with a higher order cuprate, to form the syn-SN2 product 159 exclusively [74]. The lithi-ated carbamate is assumed to coordinate the cuprate reagent (see 160), which forces the syn attack and gives trans-menthene (159). [Pg.211]


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See also in sourсe #XX -- [ Pg.439 ]




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