Ring Opening of Epoxides by Pendant Silanols

Review Chemistry, Organic

Recent Advances on Catalytic Osmium-Free Olefin syn-Dihydroxylation

Thierry Achard et al.

Summary: This minireview explores recent advances in the synthesis of syn-dihydroxylation of olefinic groups, focusing on osmium-free and more eco-compatible systems, specifically the direct oxidation of olefins catalyzed by transition metal complexes.

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY (2021)

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Article Chemistry, Organic

Tethered Silanoxyiodination of Alkenes

Ranjeet A. Dhokale et al.

Summary: This study presents the first examples of tethered silanoxyiodination reactions of allylic alcohols, yielding useful silanediol organoiodide synthons with high regioselectivity and diastereocontrol. The reaction is scalable without loss of yield or selectivity, and the products serve as starting materials for various transformations. DFT calculations provide insights into the excellent 6-endo selectivity of this reaction, indicating kinetically and thermodynamically favored products.

JOURNAL OF ORGANIC CHEMISTRY (2021)

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Article Biochemistry & Molecular Biology

A Formal Rearrangement of Allylic Silanols

Ranjeet A. Dhokale et al.

Summary: The study demonstrates that 1M aqueous HCl/THF or NaBH4/DMF can facilitate the demercurative ring-opening of cyclic organomercurial synthons into secondary silanol products bearing terminal alkenes. A two-step protocol allows for the rearrangement of primary allylic silanol substrates into cyclic organomercurials. Computational investigations indicate that the rearrangement is thermodynamically controlled and the di-tert-butylsilanol protecting group plays a crucial role in product selectivity.

MOLECULES (2021)

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Article Chemistry, Organic

Diarylborinic Acid-Catalyzed Regioselective Ring Openings of Epoxy Alcohols with Pyrazoles, Imidazoles, Triazoles, and Other Nitrogen Heterocycles

Shrey P. Desai et al.

Summary: This study introduced a method for regioselective ring openings of 3,4- and 2,3-epoxy alcohols with ambident nitrogen heterocycles using a diarylborinic acid catalyst. It favors a single regioisomer in couplings of nucleophile and electrophile partners that exhibit low regioselectivity under conventional conditions, providing access to aromatic heterocycles with stereochemically defined, functionalized alkyl substituents similar in structure to medicinally relevant compounds.

ORGANIC LETTERS (2021)

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Article Chemistry, Organic

Unusual rearrangement-remercuration reactions of allylic silanols

Someshwar Nagamalla et al.

Summary: The first examples of rearrangement reactions of allylic silanol substrates into linear ketone and 5-membered cyclic silanediol organomercurial products are presented in this study. The reactions are mediated by Hg(OTf)(2) and show differences in the use of base, solvent, and temperature. Mechanistic studies suggest that these products result from a series of cascading transformations in one pot, with a DFT analysis providing insights into the rearrangement process.

ORGANIC CHEMISTRY FRONTIERS (2021)

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Article Chemistry, Applied