The desymmetrizing hydroformylation of internal alkenes derived from dihydromuconic acid is described. The study of this reaction afforded easy access to polyfunction aldehydes. After the evaluation of the reactivity of the dimethyl ester derivative with various primary amines, this methodology was used to design a rapid synthesis of (±)-vindeburnol from tryptamine in only two steps.
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http://dx.doi.org/10.1021/acs.joc.6b02939 | DOI Listing |
J Org Chem
February 2017
Laboratoire d'Innovation Thérapeutique, UMR7200 CNRS/Université de Strasbourg, Faculté de Pharmacie , 74 route du Rhin, 67412 Illkirch, France.
The desymmetrizing hydroformylation of internal alkenes derived from dihydromuconic acid is described. The study of this reaction afforded easy access to polyfunction aldehydes. After the evaluation of the reactivity of the dimethyl ester derivative with various primary amines, this methodology was used to design a rapid synthesis of (±)-vindeburnol from tryptamine in only two steps.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
May 2016
Key Laboratory of Biomedical Polymers of Ministry of Education & College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, Hubei, 430072, China.
Excellent enantioselectivities (up to 97 % ee) and diastereoselectivities (up to >99:1 d.r.) have been achieved in the desymmetrization of cyclopentenes by catalytic hydroformylation.
View Article and Find Full Text PDFChem Commun (Camb)
December 2008
Institut für Organische Chemie und Biochemie, Albert-Ludwigs-Universität Freiburg, Albertstr. 21, 79104 Freiburg, Germany.
A practical one-pot process involving a desymmetrizing hydroformylation with the aid of a chiral catalyst-directing group (CDG*), followed by a carbonyl ene cyclization provides a straightforward access to both enantiomers of the resulting cyclohexanediol; further divergent, highly selective and protecting group-free transformations furnish the carbocyclic analogues of four important 2,6-dideoxysugars.
View Article and Find Full Text PDFOrg Lett
December 2008
Institut für Organische Chemie und Biochemie, Albert-Ludwigs-Universität Freiburg, Albertstrasse 21, D-79104 Freiburg, Germany.
Rapid access to highly functionalized alkylidene cyclohexanols through a one-pot desymmetrizing hydroformylation/carbonyl ene cyclization starting from simple bisalkenylcarbinols is reported. Mechanistic insight into the carbonyl ene reaction is given, highlighting the importance of hyperconjugative substituent effects.
View Article and Find Full Text PDFOrg Lett
November 2004
Department of Chemistry, University of Manchester, Manchester M13 9PL, U.K.
Stereoselective allylation of camphor and subsequent terminal hydroformylation affords a new delta-lactol auxiliary (camTHP*OH) on multigram scale. Stereoselective condensation with glycine dimethylamide and Cbz protection affords a camTHP*-desymmetrized glycinamide building block which undergoes efficient and highly diastereoselective metal enolate alkylation reactions. Acid-mediated deprotection affords the N-Cbz-protected alpha-amino amide products which may be converted directly to alpha-amino ketones on treatment with Grignard or organolithium reagents without loss of stereochemical integrity.
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