Enantioselective Synthesis, Configurational Stability, and Reactivity of Lithium α-tert-Butylsulfonyl Carbanion Salts was written by Scholz, Roland;Hellmann, Gunther;Rohs, Susanne;Oezdemir, Diana;Raabe, Gerhard;Vermeeren, Cornelia;Gais, Hans-Joachim. And the article was included in European Journal of Organic Chemistry in 2010.Recommanded Product: Sodium 2-methyl-2-propanethiolate This article mentions the following:
The reactions of enantiopure S-tert-Bu sulfones of the type R1CH(R2)SO2tBu (≥99 % ee) with lithiumorganyl compounds gave the corresponding chiral α-sulfonyl carbanion salts [R1C(R2)SO2tBu]Li with ≥94 % ee. The enantioselectivity of the deprotonation of the phenyl- but not dialkyl-substituted sulfones is strongly dependent on the nature of the lithiumorganyl. Because of this observation and the strong decrease in enantioselectivity in the presence of TMEDA and HMPA, we propose an intramol. proton transfer following complexation of the sulfone by RLi. Racemization of [R1C(R2)SO2tBu]Li follows first-order kinetics and seems to be mainly an enthalpic process with a small neg. activation entropy, as revealed by polarimetric measurements at low temperatures This is in accordance with Cα-S bond rotation as the rate-determining step. The salts [R1C(R2)SO2tBu]Li have half-lives of racemization in the order of several hours at -105 °C. The deuteration of the salts at -105 °C with CF3CO2D proceeded with enantioselectivities of ≥94 % ee, the magnitude of which was not significantly affected by the presence of TMEDA and HMPA. The salts also reacted with carbon-based electrophiles at low temperatures with high enantioselectivity. The conversion of R1CH(R2)SO2tBu via [R1C(R2)SO2tBu]Li to R1C(R2,E)SO2tBu, which involves the loss of stereogenicity at the α-stereogenic center and its re-establishment upon reaction of the chiral carbanion with electrophiles, occurred with high overall enantioselectivity. Electrophiles attack the anionic C atom of [R1C(R2)SO2tBu]Li with high selectivity on the side syn to the O atoms and anti to the tert-Bu group. The reactivity of the dialkyl-substituted salts [R1C(R2)SO2tBu]Li (R1, R2 = alkyl) is significantly higher than that of the benzylic salts [RC(Ph)SO2tBu]Li (R = alkyl) and the HMPA-coordinated SIPs of [MeC(Ph)SO2tBu]Li are significantly more reactive towards EtI than the corresponding O-Li contact ion pairs. In the experiment, the researchers used many compounds, for example, Sodium 2-methyl-2-propanethiolate (cas: 29364-29-2Recommanded Product: Sodium 2-methyl-2-propanethiolate).
Sodium 2-methyl-2-propanethiolate (cas: 29364-29-2) belongs to alcohols. Similar to water, an alcohol can be pictured as having an sp3 hybridized tetrahedral oxygen atom with nonbonding pairs of electrons occupying two of the four sp3 hybrid orbitals. Tertiary alcohols cannot be oxidized at all without breaking carbon-carbon bonds, whereas primary alcohols can be oxidized to aldehydes or further oxidized to carboxylic acids.Recommanded Product: Sodium 2-methyl-2-propanethiolate
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