66378-56-1Relevant academic research and scientific papers
Chiral amino and imino-alcohols based on (R)-limonene
Fuscaldo, Rodrigo S.,Boeira, Eduam O.,Stieler, Rafael,Lüdtke, Diogo S.,Gregório, José R.
, p. 438 - 446 (2020/04/27)
Derivatives of the natural occurring and inexpensive terpene (R)-limonene were synthetized and completely characterized. Starting from internal olefin epoxidation, followed by epoxide opening with sodium azide and azide reduction with LiAlH4, two chiral amino-alcohols were obtained. The amino-alcohols were reacted with three different aldehydes, generating six new imino-alcohols, two of them yielding crystals suitable for X-ray diffraction characterization. The reduction of four of these compounds with LiAlH4 led to new amino-alcohols. All derivatives were obtained with good overall yields through simple reaction protocols.
Indium-mediated asymmetric Barbier-type allylations: Additions to aldehydes and ketones and mechanistic investigation of the organoindium reagents
Haddad, Terra D.,Hirayama, Lacie C.,Singaram, Bakthan
body text, p. 642 - 649 (2010/04/29)
(Chemical Equation Presented) We report a simple, efficient, and general method for the indium-mediated enantioselective allylation of aromatic and aliphatic aldehydes and ketones under Barbier-type conditions in a one-pot synthesis affording the corresponding chiral alcohol products in very good yield (up to 99%) and enantiomeric excess (up to 93%). Our method is able to tolerate various functional groups, such as esters, nitriles, and phenols. Additionally, more substituted allyl bromides, such as crotyl and cinnamyl bromide, can be used providing moderate enantioselectivity (72% and 56%, respectively) and excellent diastereoselectivity when employing cinnamyl bromide (95/5 anti/syn). However, the distereoselectivity when using crotyl bromide was poor and other functionalized allyl bromides under our method afforded low enantioselectivities for the alcohol products. In these types of indium-mediated additions, solvent plays a major role in determining the nature of the organoindium intermediate and we observed the susceptibility of some allylindium intermediates to hydrolysis in protic solvents. Under our reaction conditions using a polar aprotic solvent, we suggest that an allylindium(III) species is the active allylating intermediate. In addition, we have observed the presence of a shiny, indium(0) nugget throughout the reaction, irrespective of the stoichiometry, indicating disproportionation of indium halide byproduct formed during the reaction.
Enantioselective alkynylations of aromatic and aliphatic aldehydes catalyzed by terpene derived chiral amino alcohols
Watts, Cian Christopher,Thoniyot, Praveen,Hirayama, Lacie C.,Romano, Talia,Singaram, Bakthan
, p. 1829 - 1835 (2007/10/03)
Enantioselective alkynyl zinc additions to aromatic and aliphatic aldehydes have been studied using terpene derived chiral amino alcohol ligands. The limonene derived amino alcohol (1R,2R,5S)-2-methyl-5-(1-methylethenyl)-2-(1- pyrrolidinyl)cyclohexanol ga
