119784-86-0Relevant academic research and scientific papers
The influence of α-coordinating groups of aldehydes on E/Z-selectivity and the use of quaternary ammonium counter ions for enhanced E-selectivity in the Julia–Kocienski reaction
Rehman, Mintu,Surendran, Sravya,Siddavatam, Nagendra,Rajendar, Goreti
supporting information, p. 329 - 333 (2022/01/20)
Modified reaction conditions for improved E-selectivity of olefins in the Julia–Kocienski reaction of aldehydes having α-coordinating substituents are demonstrated. The chelating groups in aldehydes are expected to stabilize the syn-transition state with metal ions, whereas the weakly coordinating quaternary ammonium ions are devoid of all possible chelating interactions to enhance E-selectivity. A systematic investigation is presented to study the size of the neighbouring protecting groups of aldehydes and their chelation effect on E/Z-selectivity in the Julia–Kocienski reaction.
Alkylation of thiols with trichloroacetimidates under neutral conditions
Duffy, Brian C.,Howard, Kyle T.,Chisholm, John D.
supporting information, p. 3301 - 3305 (2015/03/04)
Trichloroacetimidates are displaced with thiols to form the corresponding sulfides without the need for an added acid or base by simply heating the reactants in refluxing THF. This operationally simple procedure provides the corresponding sulfides in excellent yields with only the formation of the neutral trichloroacetamide as the side product. The imidate may also be formed in situ, allowing for a direct method for the formation of sulfides from alcohols. This reaction provides a general method for the synthesis of a variety of sulfides from inexpensive and readily available alcohol starting materials.
Total synthesis and proof of relative stereochemistry of (-)-aureonitol
Jervis, Peter J.,Cox, Liam R.
, p. 7616 - 7624 (2008/12/22)
(Chemical Equation Presented) Two trisubstituted epimeric tetrahydrofurans, 1 and 2, have been synthesized in order to confirm the relative stereochemistry in the natural product aureonitol. The key step in the synthesis of 1 and 2 involved a stereoselective intramolecular allylation of an allylsilane with an aldehyde, which introduced the stereotriad in the five-membered ring. The major tetrahydrofuran diastereoisomer 18 from this cyclization reaction was subsequently elaborated to tetrahydrofuran 1. Its 3-epimer (2) was then prepared from 1 via an oxidation-reduction sequence. Compound 1 exhibits identical 1H NMR data to those reported for aureonitol, which was isolated from Helichrysum aureonitons by Bohlmann in 1979, whereas the 1H NMR data for 2 are markedly different. The 1H NMR data (in CDCl3, CD3OD, and C6D6) and 13C NMR data (in CDCl3) for 1 are also identical with those reported for a natural product isolated from various Chaetomium sp. by Abraham, Seto, and Teuscher. These findings support Abraham's conclusion that the structure of aureonitol should be revised from 2 to 1. The enantioselective synthesis of 1 has also confirmed that (-)-aureonitol isolated by Abraham contains the (2S,3R,4S) absolute configuration of stereocenters on the tetrahydrofuran ring.
SINGLE-STEP PREPARATION OF ALLYLIC SULFIDES HAVING 1-PHENYLTETRAZOLE-5-THIO GROUP FROM ALLYLIC ALCOHOLS USING S,S'-BIS(1-PHENYL-1H-TETRAZOL-5-YL) DITHIOCARBONATE AND REACTIONS INVOLVING THE ALLYLIC SULFIDES
Takeda, Kazuyoshi,Tsuboyama, Kanoko,Torii, Katsumi,Murata, Maki,Ogura, Haruo
, p. 4105 - 4108 (2007/10/02)
The reaction of allylic alcohols and S,S'-bis(1-phenyl-1H-tetrazol-5-yl) dithiocarbonate (1) gave allylic sulfides having 1-phenyltetrazole-5-thio group in a single step.Furthermore, these allylic sulfides could be applied to carbon-carbon bond and carbon-sulfur bond formations by using Grignard reagents or carbanions in the presence of catalytic amount of copper(I) bromide or palladium (0), respectively.
