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Catalytic dinitrogen reduction to hydrazine and ammonia using Cr(N₂)₂(diphosphine)₂ complexes

https://doi.org/10.1039/d4dt00702f

Beasley, Charles H; Duletski, Olivia L; Stankevich, Ksenia S; Arulsamy, Navamoney; Mock, Michael T (March 2024, Dalton Transactions)

Cr(N₂)₂(diphosphine)₂ complexes catalyze the reduction of dinitrogen at room temperature using SmI₂ and ethylene glycol or H₂O to form hydrazine and ammonia.
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A Highly Stereospecific Claisen–Sakurai Approach to Densely Functionalized Cyclopentenols

https://doi.org/10.1021/acs.joc.2c01397

Stankevich, Ksenia S.; Cook, Matthew J. (September 2022, The Journal of Organic Chemistry)

The formation of highly substituted cyclopentenols was developed using a Claisen−Sakurai reaction. Both elements of the reaction can be performed in a one-pot sequence that provides the corresponding cyclized products in high stereoselectivity. The stereochemical outcome is defined by a combination of Claisen stereospecificity and stereoelectronic effects in the Sakurai cyclization that promotes reactivity via an anti-SE′ antiperiplanar transition state. This was determined by examination of the product stereochemistry and through detailed DFT analysis.
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Highly diastereo- and branched-selective rearrangement of substituted N -alloc- N -allyl ynamides

https://doi.org/10.1039/d2cc03399b

Jackson, Oliver D.; Stankevich, Ksenia S.; Cook, Matthew J. (October 2022, Chemical Communications)

An auto-tandem catalytic, branched-selective rearrangement of substituted N-alloc-N-allyl ynamides was developed. This reaction provides ready access to complex quaternary nitrile products with vinylogous stereocentres in excellent diastereoselectivity, including contiguous all-carbon quaternary centres. The stereochemical outcome is determined via a Pd(0) catalysed dipolar ketenimine aza-Claisen rearrangement and computational studies exemplify the key role ligand geometry plays.
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Pd-Catalyzed Rearrangement of N -Alloc- N -allyl Ynamides via Auto-Tandem Catalysis: Evidence for Reversible C–N Activation and Pd(0)-Accelerated Ketenimine Aza-Claisen Rearrangement

https://doi.org/10.1021/acs.orglett.0c04078

Alexander, Juliana R.; Shchepetkina, Veronika I.; Stankevich, Ksenia S.; Benedict, Rory J.; Bernhard, Samuel P.; Dreiling, Reagan J.; Cook, Matthew J. (January 2021, Organic Letters)
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