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• W1987714249 endingPage "2135" @default.
• W1987714249 startingPage "2119" @default.
• W1987714249 abstract "The reaction between certain aryl bromides RBr having substituents with group 14 elements and magnesium in THF to form the corresponding Grignard reagents RMgBr were found to be accompanied by unusual migrations of the group 14 functionality; it partially exchanges position with that of the original aryl bromide function. This migration is purely intramolecular for organosilicon derivatives but both intra- and intermolecular for the corresponding tin compounds. For example, 1-bromo-2-((trimethylsilyl)methyl)benzene (1b) gives rise to 1-(bromomagnesio)-2-((trimethylsilyl)methyl)benzene (2b) and to its intramolecular rearrangement product 1-((bromomagnesio)methyl)-2-(trimethylsilyl)benzene (3b), whereas the trimethylstannyl analogue 1a forms, in addition to the two corresponding Grignard reagents 2a and 3a formed by the intramolecular pathway, the intermolecular exchange products 1-(trimethylstannyl)-2-((trimethylstannyl)methyl)benzene (4a) and 1-(bromomagnesio)-2-((bromomagnesio)methyl)benzene (5‘). These results, together with those from analogous reactions of compounds such as 1-bromo-2-(trimethylstannyl)benzene (18), its 5-methyl derivative 23, 2-bromo-2‘-(trimethylstannyl)biphenyl (40), and its silicon analogue 57, can be convincingly explained by invoking the intermediate formation of the highly reactive carbanion R:-, which may in some cases be slightly stabilized by formation of an (intra- or intermolecular) stannate (or silicate) complex. Another serious candidate for such migrations would have been the radical R•, the occurrence of which is well-documented in Grignard reactions. However, this alternative route could be excluded by producing this radical in an unambiguous fashion from 1a and samarium(II) diiodide; under these conditions, hydrogen abstraction by R• strongly predominated, and minor quantities of rearranged products were shown to be due to further reduction of R• to R:-." @default.
• W1987714249 created "2016-06-24" @default.
• W1987714249 creator A5005824221 @default.
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• W1987714249 creator A5047189880 @default.
• W1987714249 creator A5054274726 @default.
• W1987714249 creator A5070010505 @default.
• W1987714249 date "2002-04-19" @default.
• W1987714249 modified "2023-10-17" @default.
• W1987714249 title "Carbanions as Intermediates in the Formation of Grignard Reagents" @default.
• W1987714249 cites W1531381054 @default.
• W1987714249 cites W1963624334 @default.
• W1987714249 cites W1963982778 @default.
• W1987714249 cites W1965722887 @default.
• W1987714249 cites W1969668614 @default.
• W1987714249 cites W1970128626 @default.
• W1987714249 cites W1970157617 @default.
• W1987714249 cites W1972563163 @default.
• W1987714249 cites W1976713737 @default.
• W1987714249 cites W1978250512 @default.
• W1987714249 cites W1978505378 @default.
• W1987714249 cites W1979168818 @default.
• W1987714249 cites W1980982360 @default.
• W1987714249 cites W1984156217 @default.
• W1987714249 cites W1985096050 @default.
• W1987714249 cites W1987399446 @default.
• W1987714249 cites W1989170531 @default.
• W1987714249 cites W1990058986 @default.
• W1987714249 cites W1991354532 @default.
• W1987714249 cites W1993251171 @default.
• W1987714249 cites W1994413410 @default.
• W1987714249 cites W1994485733 @default.
• W1987714249 cites W1999139342 @default.
• W1987714249 cites W2000731013 @default.
• W1987714249 cites W2000918285 @default.
• W1987714249 cites W2002210277 @default.
• W1987714249 cites W2002322172 @default.
• W1987714249 cites W2003433226 @default.
• W1987714249 cites W2003849042 @default.
• W1987714249 cites W2008355690 @default.
• W1987714249 cites W2010042818 @default.
• W1987714249 cites W2011640723 @default.
• W1987714249 cites W2013936951 @default.
• W1987714249 cites W2014301253 @default.
• W1987714249 cites W2015209727 @default.
• W1987714249 cites W2019345015 @default.
• W1987714249 cites W2023022455 @default.
• W1987714249 cites W2023853735 @default.
• W1987714249 cites W2027857047 @default.
• W1987714249 cites W2029942958 @default.
• W1987714249 cites W2038755160 @default.
• W1987714249 cites W2039926029 @default.
• W1987714249 cites W2043378107 @default.
• W1987714249 cites W2043888573 @default.
• W1987714249 cites W2045783720 @default.
• W1987714249 cites W2046234786 @default.
• W1987714249 cites W2046445923 @default.
• W1987714249 cites W2048028760 @default.
• W1987714249 cites W2053798268 @default.
• W1987714249 cites W2066863002 @default.
• W1987714249 cites W2067598887 @default.
• W1987714249 cites W2074508342 @default.
• W1987714249 cites W2076301309 @default.
• W1987714249 cites W2076689898 @default.
• W1987714249 cites W2076778658 @default.
• W1987714249 cites W2078287650 @default.
• W1987714249 cites W2079275349 @default.
• W1987714249 cites W2079803064 @default.
• W1987714249 cites W2082092735 @default.
• W1987714249 cites W2082815458 @default.
• W1987714249 cites W2086313783 @default.
• W1987714249 cites W2089097794 @default.
• W1987714249 cites W2091365514 @default.
• W1987714249 cites W2094730082 @default.
• W1987714249 cites W2096708867 @default.
• W1987714249 cites W2107533853 @default.
• W1987714249 cites W2109624089 @default.
• W1987714249 cites W2110330186 @default.
• W1987714249 cites W2112202244 @default.
• W1987714249 cites W2118989236 @default.
• W1987714249 cites W2119926231 @default.
• W1987714249 cites W2128242291 @default.
• W1987714249 cites W2159242371 @default.
• W1987714249 cites W2169379084 @default.
• W1987714249 cites W2277120651 @default.
• W1987714249 cites W2312832890 @default.
• W1987714249 cites W2313802200 @default.
• W1987714249 cites W2318487926 @default.
• W1987714249 cites W2319916043 @default.
• W1987714249 cites W2324429641 @default.
• W1987714249 cites W2336012611 @default.
• W1987714249 cites W2949566354 @default.
• W1987714249 cites W2949816861 @default.
• W1987714249 cites W2949944264 @default.
• W1987714249 cites W2950801076 @default.
• W1987714249 cites W2951981084 @default.
• W1987714249 cites W2952539107 @default.

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