1730-92-3Relevant articles and documents
Naphthyl 3,4,6-tri-O-methyl-β-D-glucopyranoside as a chiral auxiliary in an asymmetric 1,4-addition reaction
Chiappe, Cinzia,Lo Moro, Giacomo,Munforte, Paola
, p. 2311 - 2317 (1997)
Naphthyl 3,4,6-tri-O-methyl-β-D-glucopyranoside, easily synthesized from tri-O-acetyl-D-glucal, has been applied as a chiral auxiliary in an asymmetric Michael addition to the 2-O-crotonate. A very high facial diastereoselection (>95%) was obtained. No diastereoselection was observed when 1,3,4,6-tetra-O-methyl-β-D-glucopyranoside was used as the chiral auxiliary. A stereochemical model, taking into account steric shielding and π-stacking effects, is proposed on the basis of the observed results.
Effect of chiral substituents on the secondary structure of poly(N-alkynylamides)
Tabei, Junichi,Shiotsuki, Masashi,Sanda, Fumio,Masuda, Toshio
, p. 5860 - 5867 (2005)
Optically active N-alkynylamides (S)-HC≡C(CH2) aNHCO(CH2)bCH(CH3)CH 2CH3 (1: a = 1, b = 0; 2: a = 1, b = 1; 3: a = 1, b = 2; 4: a = 1, b = 3; 5: a = 2, b = 0; 6: a = 2, b = 1; 7: a = 3, b = 0), having several numbers of methylene spacers between the ethynyl group and chiral carbon or amide group, and (S)-HC≡C(CH2)2OCOCH 2CH(CH3)CH2CH3 (8) were polymerized with (nbd)Rh+[η6-C6H5B --(C6H5)3] to afford the corresponding polymers with moderate molecular weights (Mn = 11 000-21 000) in 67-99% yields. The 1H NMR spectra demonstrated that the resulting polymers had stereoregular structures (cis content = 79-100%). CD, UV-vis, and IR spectroscopic studies revealed that the position of the amide group and chiral center strongly affects the pitch and stability of helical structure of the polymers, and intramolecular hydrogen bonding is formed between the amide groups in CHCl3. By comparison with the results of CD measurements and molecular orbital calculation, the sign of Cotton effect and the relationship between the screw sense of poly(N-propargylamides) was elucidated.
Novel iridium complex of spirophosphine-carboxylic acid, preparation method and application thereof
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Paragraph 0076; 0077; 0079, (2017/05/20)
The invention relates to an iridium complex of spirophosphine-carboxylic acid, a preparation method and application thereof. The iridium complex of spirophosphine-carboxylic acid is a compound with a structure shown as formula (I), wherein n=0-3; and the values of R1, R2, R3, R4, R5, R6 and R7 are defined as claim 1. Substituted 7-carboxyl-7'-diarylphosphino-1, 1'-spirobiindane is taken as the ligand to from carboxylic acid anion under the action of alkali, and then complexation with an iridium precursor is carried out to obtain different iridium/spirophosphine-carboxylic acid complexes. The iridium complex of spirophosphine-carboxylic acid provided by the invention can catalyze the asymmetric hydrogenation reaction of a variety of unsaturated carboxylic acids, and show high activity and enantioselectivity, thus having good industrialization prospects. (formula (I)).
Synthesis of Polysubstituted γ-Butenolides via a Radical Pathway: Cyclization of α-Bromo Aluminium Acetals and Comparison with the Cyclization of α-Bromoesters at High Temperature
Bénéteau, Romain,Despiau, Carole F.,Rouaud, Jean-Christophe,Boussonnière, Anne,Silvestre, Virginie,Lebreton, Jacques,Dénès, Fabrice
supporting information, p. 11378 - 11386 (2015/08/03)
Polysubstituted butenolides were obtained in good to high yields from α-bromoesters derived from propargyl alcohols by a one-pot reaction involving the radical cyclization of α-bromo aluminium acetals, followed by the oxidation of the resulting cyclic aluminium acetals in an Oppenauer-type process and migration of the exocyclic C-C bond into the α,β-position. Comparison with the direct cyclization of α-bromoesters at high temperature and under high dilution conditions is described. Deuterium-labelling experiments allowed us to uncover "invisible" 1,5-hydrogen atom transfers (1,5-HATs) that occur during these cyclization processes, together with the consequences of the latter in the epimerization of stereogenic centres. Compared to the classical approach, the cyclization of aluminium acetals proved to be highly chemoselective and its efficiency was illustrated by the short total syntheses of optically enriched γ-butenolides isolated from Plagiomnium undulatum and from Kyrtuhrix maculans.