129171-89-7Relevant academic research and scientific papers
Facile separation of diastereo-chiral N,N′-diamine ligand via fractional crystallization and demetalation of corresponding Zn(II) complex
Nayab, Saira,Jeong, Jong Hwa
, p. 35 - 38 (2016)
Enantiopure N,N-diamine has been obtained in an economical manner via demetalation of its corresponding dichloro Zn(II) complex, which is separated by fractional crystallization of two diastereomeric Zn(II) complexes. Polymerization of rac-lactide (rac-LA
Chiral 1,3,2-Diazaphospholenes as Catalytic Molecular Hydrides for Enantioselective Conjugate Reductions
Miaskiewicz, Solène,Reed, John H.,Donets, Pavel A.,Oliveira, Caio C.,Cramer, Nicolai
supporting information, p. 4039 - 4042 (2018/03/13)
Secondary 1,3,2-diazaphospholenes have a polarized P?H bond and are emerging as molecular hydrides. Herein, a class of chiral, conformationally restricted methoxy-1,3,2-diazaphospholene catalysts is reported. We demonstrate their catalytic potential in asymmetric 1,4-reductions of α,β-unsaturated carbonyl derivatives, including enones, acyl pyrroles, and amides, which proceeded in enantioselectivities of up to 95.5:4.5 e.r.
Enantioselective C-H Functionalization-Addition Sequence Delivers Densely Substituted 3-Azabicyclo[3.1.0]hexanes
Pedroni, Julia,Cramer, Nicolai
supporting information, p. 12398 - 12401 (2017/09/25)
An enantioselective C-H functionalization route to perfluoroalkyl-containing 3-azabicyclo[3.1.0]hexanes is disclosed. A modular and bench-stable diazaphospholane ligand enables highly enantioselective Pd(0)-catalyzed cyclopropane C-H functionalization using trifluoroacetimidoyl chlorides as electrophilic partners. In turn, the resulting cyclic ketimine products react smoothly with a broad variety of nucleophiles in one-pot processes enabling the rapid and modular construction of heavily substituted pyrrolidines.
Asymmetric Imine Hydroboration Catalyzed by Chiral Diazaphospholenes
Adams, Matt R.,Tien, Chieh-Hung,McDonald, Robert,Speed, Alexander W. H.
supporting information, p. 16660 - 16663 (2017/12/13)
The first use of diazaphospholenes as chiral catalysts has been demonstrated with enantioselective imine hydroboration. A chiral diazaphospholene prepared in a simple three-step synthesis from commercial materials has been shown to achieve the highest enantioselectivity for the hydroboration of alkyl imines with pinacolborane reported to date. Enantiomer ratios of up to 88:12 were obtained with low (2 mol %) catalyst loadings. Twenty examples of asymmetric reduction employing this main-group catalysis protocol, including the synthesis of the pharmaceuticals ent-rasagiline and fendiline, are shown.
Diaminophosphine oxide ligand enabled asymmetric nickel-catalyzed hydrocarbamoylations of alkenes
Donets, Pavel A.,Cramer, Nicolai
supporting information, p. 11772 - 11775 (2013/09/02)
Chiral trivalent phosphorus species are the dominant class of ligands and the key controlling element in asymmetric homogeneous transition-metal catalysis. Here, novel chiral diaminophosphine oxide ligands are described. The arising catalyst system with nickel(0) and trimethylaluminum efficiently activates formamide C-H bonds under mild conditions providing pyrrolidones via intramolecular hydrocarbamoylation in a highly enantioselective manner with as little as 0.25% mol catalyst loading. Mechanistically, the secondary phosphine oxides behave as bridging ligands for the nickel center and the Lewis acidic organoaluminum center to give a heterobimetallic catalyst with superior reactivity.
Improved chiral olefin metathesis catalysts: Increasing the thermal and solution stability via modification of a C1-symmetrical N-heterocyclic carbene ligand
Savoie, Jolaine,Stenne, Brice,Collins, Shawn K.
supporting information; experimental part, p. 1826 - 1832 (2011/02/26)
Four new ruthenium-based olefin metathesis catalysts that possess an N-heterocyclic carbene (NHC) ligand with benzyl (Bn) or or n-propyl (n-Pr) N-alkyl groups have been prepared. The synthetic routes developed for the synthesis of the required dihydroimid
Design, development, and scale-up of a selective meso-epoxide desymmetrization process
Varie, David L.,Beck, Christopher,Borders, Sandra K.,Brady, Molly D.,Cronin, Jason S.,Ditsworth, Tracy K.,Hay, David A.,Hoard, David W.,Hoying, Richard C.,Linder, Ryan J.,Miller, Richard D.,Moher, Eric D.,Remacle, Jacob R.,Rieck III, John A.,Anderson, David D.,Dodson, Paul N.,Forst, Mindy B.,Pierson, Duane A.,Turpin, Joseph A.
, p. 546 - 559 (2012/12/31)
A pilot-plant scale desymmetrization of the cyclic meso-epoxide 4b, using a chiral lithium amide prepared from symmetrical diamine 17, was designed and implemented to provide allylic alcohol 3b in high yield and greater than 99% ee. This chiral alcohol was converted to ketone 2b, a key intermediate in a new asymmetric synthesis of LY459477. Chiral diamine 17 was prepared from a readily available chiral precursor, (R)-α-methylbenzylamine, and could be recovered from the reaction mixture and reused. Studies performed to probe the mechanism of the rearrangement reaction of epoxide 4b showed that diamine 17 provided an optimal combination of selectivity and scaleability for this process.
Use of diamines containing the α-phenylethyl group as chiral ligands in the asymmetric hydrosilylation of prochiral ketones
Mastranzo, Virginia M.,Quintero, Leticia,De Parrodi, Cecilia Anaya,Juaristi, Eusebio,Walsh, Patrick J.
, p. 1781 - 1789 (2007/10/03)
Chiral diamines 1-7 were used in the enantioselective hydrosilylation of prochiral aromatic and aliphatic ketones. Some of these ligands combine chiral backbones and chiral N,N′-α-phenylethyl substituents that give rise to synergistic effects between these two groups and lead to catalysts that exhibit high enantioselectivity.
