Hydrazone and Oxime Olefination via Ruthenium Alkylidenes

We describe the development of an efficient method for the olefination of hydrazones and oximes. The key design approach that enables this transformation is tuning of the energy/polarity of C=N π-bonds by employing heteroatom functionalities (NR2, OR). The resulting hydrazones or oximes facilitate olefination with ruthenium alkylidenes. Through this approach, we show that air-stable, commercially available ruthenium alkylidenes provide access to functionalized alkenes (20 examples) in ring-closing reactions with yields up to 88 %.Olefination of carbon–heteroatom double bonds is a powerful approach to access highly functionalized olefins. An approach is reported here that uses air-stable and commercially available ruthenium alkylidenes to promote C=N/olefin ring closure. The enabling strategy for this reaction is the use of hydrazones and oximes as readily accessible substrates that preferentially react with ruthenium alkylidenes, even in the presence of carbonyl groups.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/172859/1/anie202112101-sup-0001-misc_information.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/172859/2/anie202112101_am.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/172859/3/anie202112101.pd

Hydrazone and Oxime Olefination via Ruthenium Alkylidenes

We describe the development of an efficient method for the olefination of hydrazones and oximes. The key design approach that enables this transformation is tuning of the energy/polarity of C=N π-bonds by employing heteroatom functionalities (NR2, OR). The resulting hydrazones or oximes facilitate olefination with ruthenium alkylidenes. Through this approach, we show that air-stable, commercially available ruthenium alkylidenes provide access to functionalized alkenes (20 examples) in ring-closing reactions with yields up to 88 %.Olefination of carbon–heteroatom double bonds is a powerful approach to access highly functionalized olefins. An approach is reported here that uses air-stable and commercially available ruthenium alkylidenes to promote C=N/olefin ring closure. The enabling strategy for this reaction is the use of hydrazones and oximes as readily accessible substrates that preferentially react with ruthenium alkylidenes, even in the presence of carbonyl groups.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/172797/1/ange202112101-sup-0001-misc_information.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/172797/2/ange202112101_am.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/172797/3/ange202112101.pd