Stereoselective Synthesis of Functionalized Chiral 2‐Nitrocyclohexanecarboxylic Esters via Catalytic Dienamine Addition to β‐Substituted β‐Nitroacrylates. Issue 2 (6th February 2014)

• Record Type: Journal Article
• Authors: Massolo, Elisabetta; Benaglia, Maurizio; Annunziata, Rita; Palmieri, Alessandro; Celentano, Giuseppe; Forni, Alessandra
• Is Part Of: Advanced synthesis & catalysis. Volume 356:Issue 2/3(2014)
• Page Start: 493
• Page End: 500
• Publication Date: 2014-02-06
• Subjects: Catalysis -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Chemistry -- Periodicals; Chemistry, Technical -- Periodicals; Chemistry -- Periodicals; Catalysis -- Periodicals; Technology, Pharmaceutical -- Periodicals; 547.2
• DOI: 10.1002/adsc.201301074
• Languages: English
• ISSNs: 1615-4150

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>A metal‐free stereoselective catalytic addition of <italic>in situ</italic> generated dienamine to β‐nitroacrylates has been developed. Starting from simple α, β‐unsaturated ketones, highly functionalized chiral β‐nitrocyclohexanecarboxylic esters were obtained in a single step, in good yields and up to 98% <italic>ee</italic>. By an unprecedented mechanistic pathway, starting from the synthetically readily available <italic>E‐</italic>nitroacrylate, the present methodology allowed us to obtain as major product the isomer bearing a <italic>cis</italic> relative disposition between the nitro and the ester groups, which is not accessible <italic>via</italic> a classical Diels–Alder reaction.</p> <p> <boxed-text content-type="graphic" position="anchor" orientation="portrait"> <graphic position="anchor" mimetype="image" xlink:href="ark:/27927/pgg4sr7qx56" orientation="portrait" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" /> </boxed-text> </p> </abstract>