795-36-8Relevant articles and documents
Trityl-containing alcohols—an efficient chirality transmission process from inductor to the stereodynamic propeller and their solid-state structural diversity
Górczyńska, Sylwia,Brzdonkiewicz, Aleksandra,Jelecki, Maciej,Czapik, Agnieszka,Stasiak, Bartosz,Kwit, Marcin
supporting information, (2020/02/18)
The cascade process of a dynamic chirality transmission from the permanent chirality center to the stereodynamic triphenylmethyl group has been studied for series of optically active trityl derivatives. The structural analysis, carried out with the use of complementary methods, enabled us to determine the mechanism of chirality transfer. The process of chirality transmission involves a set of weak but complementary electrostatic interactions. The induction of helicity in a trityl propeller is revealed by rising non-zero cotton effects in the area of trityl UV-absorption. The presence of an additional stereogenic center in close proximity to the trityl-containing stereogenic center significantly affects the sign and, to a lesser extent, magnitude of the respective cotton effects. Despite the bulkiness of the trityl, in the crystalline phase, the molecules under study strictly fill the space. In the crystal, molecules form aggregates stabilized by OH???O hydrogen bonds. However, the presence of two trityl groups precludes formation of OH???O hydrogen bonding. Additionally, the trityl group seems to be responsible for the formation of the solid solutions by e.g., racemates of trans- and cis-2-tritylcyclohexanol. Therefore, the trityl group acts as a supramolecular protective group, which in turn can be used in the crystal engineering.
Cyanocuprates convert carboxylic acids directly into ketones
Genna, Douglas T.,Posner, Gary H.
scheme or table, p. 5358 - 5361 (2011/12/15)
Carboxylic acids were converted directly in 56-99% yields into methyl, n-butyl, and isopropyl ketones using excess cyanocuprates R2CuLi 3 LiCN. A substrate with a stereocenter α to the carboxylic acid was converted into ketones with very little loss of enantiomeric purity. A variety of functional groups were tolerated including aryl bromides. This direct transformation of a carboxylic acid into ketone with minimal tertiary alcohol formation is proposed to involve a relatively stable copper ketal tetrahedral intermediate.
Diastereoselective Michael Additions of Chiral Imidazolidines to Trityl Enones
Seebach, Dieter,Pfammatter, Elmar,Gramlich, Volker,Bremi, Tobias,Kuehnle, Florian,et al.
, p. 1145 - 1152 (2007/10/02)
The enolates A and C of t-butyl (R)-2-t-butyl-3-methyl-4-oxo-1-imidazolidinecarboxylate (1, Boc-BMI) and of 1-t-butyl 5-methyl (2R,5S)-2-t-butyl3-methyl-1,5-imidazolidinedicarboxylate (3) and t-butyl (R)-2-t-butyl-5-lithio-3-methyl-1-imidazolidinecarboxyl