Diastereoselective Nucleophilic Addition to Aldehydes with Polar alpha- and alpha,beta-Substituents
2011 (English)In: Advanced Synthesis and Catalysis, ISSN 1615-4150, E-ISSN 1615-4169, Vol. 353, no 11-12, 2022-2036 p.Article in journal (Refereed) Published
The stereoselectivities obtained in Lewis acid-promoted Mukaiyama aldol additions and Sakurai allylations of mono-, and syn- and anti-disubstituted aldehydes possessing various polar alpha- and beta-substituents under non-chelating conditions are presented. The stereochemical outcome in the nucleophilic addition to alpha-substituted aldehydes containing an alpha-benzyloxy, alpha-fluoro or alpha-sulfonamide substituent are accurately predicted by current stereoinduction models. In contrast, the selectivitites obtained from addition of sterically demanding nucleophiles to alpha-chloro-substituted aldehydes cannot be rationalized by the same models and an alternative is discussed. The stereochemichal outcome in the additions to alpha, beta-disubstituted aldehydes is more complex and cannot be predicted using current models.
Place, publisher, year, edition, pages
2011. Vol. 353, no 11-12, 2022-2036 p.
aldol reaction, allylation, diastereoselectivity, induction model
IdentifiersURN: urn:nbn:se:kth:diva-39526DOI: 10.1002/adsc.201100173ISI: 000294179400027ScopusID: 2-s2.0-80052019661OAI: oai:DiVA.org:kth-39526DiVA: diva2:441459
QC 201109162011-09-162011-09-122013-05-03Bibliographically approved