64633-20-1Relevant academic research and scientific papers
An entry to non-racemic β-tertiary-β-amino alcohols, building blocks for the synthesis of aziridine, piperazine, and morpholine scaffolds
Narczyk, Aleksandra,Stecko, Sebastian
supporting information, p. 5972 - 5981 (2020/08/21)
A method for the preparation of enantiopure β-tert-amino alcohols bearing a tetrasubstituted C-stereocenter, as well as their conversion into selected medicinally privileged heterocyclic systems (morpholines, aziridines, piperazines) is reported. These co
Rearrangement Reactions Leading to Optically Active α,α-Disubstituted Primary Allylamines
Hennum, Martin,Odden, Hege Hortemo,Gundersen, Lise-Lotte
, p. 846 - 860 (2017/02/15)
Synthetic routes to α,α-disubstituted allylamines have been examined. Racemic compounds were conveniently prepared by thermal Overman rearrangements of primary allylic alcohols with trisubstituted double bonds, but rearrangement of these substrates using
A multicomponent Ni-, Zr-, and Cu-catalyzed strategy for enantioselective synthesis of alkenyl-substituted quaternary carbons
McGrath, Kevin P.,Hoveyda, Amir H.
supporting information, p. 1910 - 1914 (2014/03/21)
The availability of enantiomerically enriched carbonyl-containing compounds is essential to the synthesis of biologically active molecules. Since catalytic enantioselective conjugate addition (ECA) reactions directly generate the latter valuable class of molecules, the design and development of such protocols represents a compelling objective in modern chemistry. Herein, we disclose the first solution to the problem of ECA of alkenyl groups to acyclic trisubstituted enones, an advance achieved by adopting an easily modifiable and fully catalytic approach. The requisite alkenylaluminum reagents are synthesized with exceptional site- and/or stereoselectivity by a Ni-catalyzed hydroalumination process, and the necessary enones are prepared through a site- and stereoselective zirconocene-catalyzed carboalumination/acylation reaction. The all-catalytic procedure is complete within four hours, furnishing the desired products in up to 77 % overall yield and 99:1 enantiomeric ratio. One-two-three punch: Ni-catalyzed alkyne hydroalumination, Zr-catalyzed alkyne carbometalation/acylation, and Cu-catalyzed enantioselective conjugate addition are combined for accessing acyclic organic molecules that contain an alkene-substituted quaternary carbon stereogenic center. The entire process takes less than four hours and affords products in up to 77 % overall yield and 99:1 enantiomeric ratio. Copyright
Enantioselective synthesis of quaternary carbon stereogenic centers through copper-catalyzed conjugate additions of aryl- and alkylaluminum reagents to acyclic trisubstituted enones
Dabrowski, Jennifer A.,Villaume, Matthew T.,Hoveyda, Amir H.
, p. 8156 - 8159 (2013/08/23)
Acyclic quaternary carbons by conjugate addition: The first examples of catalytic enantioselective conjugate additions of aryl and alkyl units that generate acyclic all-carbon quaternary stereogenic centers have been developed (see scheme). The requisite
A Stereoselective Synthesis of (E)-α,β-Unsaturated Ketones Involving the Reactions of Organocerium Reagents with Secondary β-Enamino Ketones
Bartoli, Giuseppe,Marcantoni, Enrico,Petrini, Marino,Sambri, Letizia
, p. 913 - 918 (2007/10/03)
Stereoselective construction of trisubstituted alkenes has wide applicability to the synthesis of many natural products.Specifically, β-disubstituted enones are important functionalized trisubstituted alkene targets.The reaction of organocerium reagents with secondary β-enamino ketones affords β-disubstituted α,β-unsaturated ketones in fairly good yields.This process shows considerable stereoselectivity, and α,β-unsaturated ketones of (E) configuration are predominantly observed.Organolithium-derived cerium reagents display better stereoselectivity than organomagnesium-based ones.The mechanism of the reaction varies with nitrogen substitution: N-phenyl groups give 1,2-addition products, whereas substitution products are observed with N-alkyl groups.When organocerium reagents were used with β-enamino ketones bearing secondary alkyl groups at the nitrogen atom, a lack of reactivity was observed. - Keywords: assymetric substitution; cerium reagents; enamino ketones; regioselectivity; synthetic methods
