A New Type of Stereoselectivity in Baeyer–Villiger Reactions: Access to E‐ and Z‐Olefins. Issue 1 (7th January 2013)

• Record Type: Journal Article
• Authors: Zhang, Zhi‐Gang; Roiban, Gheorghe‐Doru; Acevedo, Juan Pablo; Polyak, Iakov; Reetz, Manfred T.
• Is Part Of: Advanced synthesis & catalysis. Volume 355:Issue 1(2013)
• Page Start: 99
• Page End: 106
• Publication Date: 2013-01-07
• 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.201200759
• Languages: English
• ISSNs: 1615-4150

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>A new concept for accessing configurationally defined trisubstituted olefins has been developed. Starting from a common ketone precursor of the type 4‐ethylidenecyclohexanone, Baeyer–Villiger monooxygenases are employed as catalysts in diastereoselective Baeyer–Villiger reactions leading to the corresponding <italic>E</italic>‐ or <italic>Z</italic>‐configurated lactones. Wild‐type cyclohexanone monooxygenase (CHMO) as catalyst delivers the <italic>E</italic>‐isomers and a directed evolution mutant the opposite <italic>Z</italic>‐isomers. Subsequent transition metal‐catalyzed chemical transformations of a key product containing a vinyl bromide moiety provide a variety of different trisubstituted <italic>E‐</italic> or <italic>Z‐</italic>olefins. A model based on QM/MM sheds light on the origin of this unusual type of diastereoselectivity. In contrast to this biocatalytic approach, traditional Baeyer–Villiger reagents such as <italic>m</italic>‐CPBA fail to show any selectivity, 1:1 mixtures of <italic>E</italic>‐ and <italic>Z</italic>‐olefins being formed.</p> </abstract>