Possible Intervention of Prototropic and Silatropic Ene‐type Mechanisms in Asymmetric Catalytic Mukaiyama Aldol Reactions. Issue 1 (27th December 2013)

• Record Type: Journal Article
• Authors: Honda, Kazuya; Mikami, Koichi
• Is Part Of: Asian journal of organic chemistry. Volume 3:Issue 1(2014:Jan.)
• Page Start: 34
• Page End: 40
• Publication Date: 2013-12-27
• Subjects: Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; 547.005
• DOI: 10.1002/ajoc.201300226
• Languages: English
• ISSNs: 2193-5807

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Prototropic and silatropic ene mechanisms were analyzed in the BINOL‐Ti^IV, bisoxazoline (box)‐Cu^II, and BINAP‐Pd^II complex‐catalyzed asymmetric Mukaiyama aldol reaction of methyl glyoxylate and acetone‐derived 2‐trimethylsiloxypropene. Our ab initio calculations indicate that the BINOL‐Ti^IV‐catalyzed Mukaiyama aldol reaction proceeds through the concerted prototropic or silatropic ene pathways and that box‐Cu^II‐ and BINAP‐Pd^II‐catalyzed reactions proceed through the stepwise prototropic ene pathways. The transition‐state conformations are thus <italic>syn</italic>‐clinal with hydrogen and silane as the migratory groups aligned to the formyl oxygen atom in close <italic>syn</italic>‐clinal proximity, respectively.</p> </abstract>