Isopropylmagnesium chloride, reaction

Chlorodiisopropylsilane, Cl(i-Pr)2SiH (1). The silane is prepared in 76% yield by reaction of isopropylmagnesium chloride with trichlorosilane. 

With unsubstituted 5-iodouracil 336, a trimagnesiated species 337 can be formed by sequential treatment with methylmagnesium chloride and isopropylmagnesium chloride, and reaction with various electrophiles then selectively gives 5-functionalized uracil derivatives 338 <20070L1639>. The same procedure was also successfully applied to the functionalization of 6-iodouracils, including the synthesis of Emivirine and l-[(2-hydroxyethoxy)methyl]-6-(phenylthio)thymine (ElEPT) precursors <20070L1639>. 

In 2002, Figad re and coworkers reported the mono-reduction of 2-aryl (or heteroaryl)-1,1-dibromo-l-alkenes (Scheme 23). The reaction is achieved with one equivalent of isopropylmagnesium chloride in the presence of iron(III) acetylacetonate. Pure ( )-alkenyl bromides are obtained. With two equivalents of alkyl Grignard reagent, the mono-substituted product is obtained in moderate yield. 

The isopropyl compound V, (R = Me2CH) has readily been obtained from VI and isopropylmagnesium chloride in ether solution (94) but when R = cyclopentyl, THF has been found to be necessary for effecting the reaction. When R = tert-butyl the Grignard reaction yielded the dimer VII, but the desired V (R = er -butyl) has been obtained... 

Catalyst for DIels-Alder reaction of ynamlnes. A zero-valent iron species prepared by reduction of iron(III) chloride with isopropylmagnesium chloride serves as a unique catalyst for cycloaddition of butadiene and ynamines (1) to form 1,4-cyclohexadienamines (2). These products are hydrolyzed by mild acid treatment to (3,y-cyclohexenones (3), which are isomerized to either 4 or 5 by catalytic amounts of rhodium catalysts. 

Treatment of magnesium alkylidene carbenoids, which were generated from 1-chlorovinyl /)-tolyl sulfoxide 161 with isopropylmagnesium chloride at —78°C in toluene, with AT-lithioindazole 162 (or pyrazole) gave N-alkenylated indazole 163 in moderate yield (Scheme 5) <2005TL4855>. Reaction of lithiopyrazole gave the N-alkenylated pyrazole but in a lower yield. 

The main product in the reaction of norbornadiene with buta-1,3-diene resulted from a 1,4-cycloaddition onto the conjugated diene (for extended homo-Diels-Alder reactions, vide infra). On the other hand, the 1,2-homo-Diels-Alder adduct 4 was obtained when bisfcycloocta-tetraenejiron [or iron(III) chloride/isopropylmagnesium chloride] was used as the catalyst. ... 

Reactions are more rapid in tetrahydrofuran (THF) than in EtjO ", and addition of R3N to EtjO increases rates - . Use of hexamethylphosphoramide (HMPA) as the solvent accelerates metallation rate e.g., 1-heptyne is metallated by isopropylmagnesium chloride in cooled HMPA... 

A dialkyl-//-silanol like diisopropyl-H-silanol (537) can be obtained in 85% yield by the reaction of trichlorosilane with isopropylmagnesium chloride and subsequent hydrolysis of the formed chlorosilane 536 (equation 265)290. 

The reactions of indolyl Grignard reagents, generated in this fashion, have been explored further by others [389-392]. A regioselective Grignard formation at C2 occurred upon tteatment of 2,3-diiodo-iV-(phenylsulfonyl)indole (28) with isopropylmagnesium chloride [393]. 

The Bu2/PrMgLi complex, generated by the reaction of butyllithium with isopropylmagnesium chloride in a 2 1 ratio, was shown to carry out the... 

Indene added to ethereal isopropylmagnesium chloride, then hexamethylphosphoramide added dropwise, heated 1 hr. to complete the reaction, the ether removed by distillation, a 1 1 mixture of diethyl sulfate and hexamethylphosphoramide added, and heated slowly to 80 during 7 hrs. -> 3-ethylindene. Y 92%. F. syntheses s. T. Guvigny and H. Normant, Bl. 196A, 2000 exchange reaction, comparison of solvents, cf. J.-J. Delpuech, Tetrah. Let. 1965, 2111. 

Preparative Method obtained by reaction of trichlorosilane with isopropylmagnesium chloride the original yield of 45% may be raised to 70-80% by employing cone hydrochloric acid to quench the reaction. ... 

Halogen-Magnesium Exchange Reaction of Alkenyl Iodides. The reaction of alkenyl iodides with isopropylmagnesium chloride-lithium chloride is one of the best ways to prepare functionalized alkenylmagnesium reagents. This reaction is... 

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