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• W2017146469 abstract "Modern organic synthesis (e.g., of natural products) is virtually impossible without employment of enantiomerically enriched compounds. In many cases, alkyllithium compounds are key intermediates for the generation of these stereogenic substances. In recent years, the lithiated carbon atom in silicon-substituted benzyllithium compounds has become a focus of interest because it is possible to maintain its stereogenic information. Starting from a highly enantiomerically enriched benzylsilane, (R,S)-2 x quinuclidine could be obtained, and the absolute configuration at the metalated carbon atom was determined by X-ray diffraction analysis. In solution, a quartet was found in the (13)C NMR spectrum for the metalated carbon atom because of coupling between carbon and lithium, indicating a fixed lithium carbon contact at room temperature. After reaction of (R,S)-2 x quinuclidine with trimethylchlorostannane, the trapped product (S,S)-4 was obtained with a dr > or = 98:2 with inversion of the configuration at the metalated carbon. Multipole refinement against high-resolution diffraction data and subsequent topological analysis of the benchmark system (R,S)-2 x quinuclidine provide insight in the electronic situation and thus the observed stereochemical course of the transformations. Surprisingly, the negative charge generated at the carbanion hardly couples into the phenyl ring. The neighboring silicon atom counterbalances this charge by a pronounced positive charge. Therefore, the alpha-effect of the silicon atom is caused not just by a polarization of the electron density but also by an electrostatic bond reinforcement. Furthermore, the experimentally determined electrostatic potential unequivocally explains the observed back side attack of an electrophile under inversion of the stereogenic center with high diastereomeric ratios." @default.
• W2017146469 created "2016-06-24" @default.
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• W2017146469 date "2008-08-15" @default.
• W2017146469 modified "2023-10-09" @default.
• W2017146469 title "Structure/Reactivity Studies on an α-Lithiated Benzylsilane: Chemical Interpretation of Experimental Charge Density" @default.
• W2017146469 cites W1503838212 @default.
• W2017146469 cites W1849413563 @default.
• W2017146469 cites W1971572838 @default.
• W2017146469 cites W1974145294 @default.
• W2017146469 cites W1975395323 @default.
• W2017146469 cites W1976573601 @default.
• W2017146469 cites W1977535094 @default.
• W2017146469 cites W1983436447 @default.
• W2017146469 cites W1985837948 @default.
• W2017146469 cites W1986046390 @default.
• W2017146469 cites W1988765270 @default.
• W2017146469 cites W1989390095 @default.
• W2017146469 cites W1997630655 @default.
• W2017146469 cites W2000249116 @default.
• W2017146469 cites W2000377033 @default.
• W2017146469 cites W2001803280 @default.
• W2017146469 cites W2003291017 @default.
• W2017146469 cites W2004772572 @default.
• W2017146469 cites W2005148229 @default.
• W2017146469 cites W2005461424 @default.
• W2017146469 cites W2011771321 @default.
• W2017146469 cites W2012145526 @default.
• W2017146469 cites W2013763166 @default.
• W2017146469 cites W2016373492 @default.
• W2017146469 cites W2016824809 @default.
• W2017146469 cites W2018142060 @default.
• W2017146469 cites W2022474922 @default.
• W2017146469 cites W2022654278 @default.
• W2017146469 cites W2023874741 @default.
• W2017146469 cites W2026639976 @default.
• W2017146469 cites W2030553189 @default.
• W2017146469 cites W2033365705 @default.
• W2017146469 cites W2033480557 @default.
• W2017146469 cites W2034445098 @default.
• W2017146469 cites W2035025542 @default.
• W2017146469 cites W2036344795 @default.
• W2017146469 cites W2044529655 @default.
• W2017146469 cites W2050518392 @default.
• W2017146469 cites W2058746678 @default.
• W2017146469 cites W2061357532 @default.
• W2017146469 cites W2061950648 @default.
• W2017146469 cites W2068802714 @default.
• W2017146469 cites W2070344509 @default.
• W2017146469 cites W2071549017 @default.
• W2017146469 cites W2074921157 @default.
• W2017146469 cites W2080147054 @default.
• W2017146469 cites W2082866103 @default.
• W2017146469 cites W2085377744 @default.
• W2017146469 cites W2085862871 @default.
• W2017146469 cites W2087192962 @default.
• W2017146469 cites W2088047248 @default.
• W2017146469 cites W2088995382 @default.
• W2017146469 cites W2094811133 @default.
• W2017146469 cites W2103466293 @default.
• W2017146469 cites W2106999152 @default.
• W2017146469 cites W2109286706 @default.
• W2017146469 cites W2125780345 @default.
• W2017146469 cites W2126974386 @default.
• W2017146469 cites W2128179591 @default.
• W2017146469 cites W2130271093 @default.
• W2017146469 cites W2131350133 @default.
• W2017146469 cites W2133083976 @default.
• W2017146469 cites W2139863019 @default.
• W2017146469 cites W2139881842 @default.
• W2017146469 cites W2146450525 @default.
• W2017146469 cites W2150166110 @default.
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• W2017146469 cites W2163398637 @default.
• W2017146469 cites W2496346391 @default.
• W2017146469 cites W2951987027 @default.
• W2017146469 cites W3005425261 @default.
• W2017146469 cites W3143532597 @default.
• W2017146469 cites W4205366255 @default.
• W2017146469 cites W4206723897 @default.
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• W2017146469 doi "https://doi.org/10.1021/ja711104q" @default.
• W2017146469 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/18702464" @default.
• W2017146469 hasPublicationYear "2008" @default.
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