Journal
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
Volume 2020, Issue 35, Pages 5752-5764Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/ejoc.202000976
Keywords
Ketene heterodimer; Deoxypropionate; Hydrogenation; Heterogeneous catalysis; Diastereoselectivity
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Funding
- National Science Foundation (US)
- National Institutes of Health (US) [CHE-1463728, R15GM107800]
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Catalytic hydrogenolysis of theZ-isomer of a series of aryl-substituted ketene heterodimer beta-lactones facilitated access to deoxypropionate derivatives with adrranging from 54:46 to 86:14, favoring theanti-isomer, and with excellent transfer of chirality (91 -> 99 %eefor 13 examples). Although X = 4-F was determined to provide optimal diastereoselectivity (dr86:14), a non-linear relationship between diastereoselectivity and aryl substituent sigma values was found. For cases where apara- orortho-EWG was present on the aryl ring of the ketene heterodimer, formation of significant amounts of beta-lactone (20-44 %) as by-product was observed. The results of a number of control reactions point toanti-beta-elimination and ananti-selective hydrogenation of anE-isomer olefin intermediate being key steps in the reaction mechanism. The synthetic potential of the deoxypropionate derivative products was demonstrated by oxidative conversion into a 1,5-difunctionalized deoxypropionate motif.
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