Stannyl-Lithium: A Facile and Efficient Synthesis Facilitating Further Applications

Abstract

We have developed a highly efficient, practical, polycyclic aromatic hydrocarbon (PAH)-catalyzed synthesis of stannyl lithium (Sn-Li), in which the tin resource (stannyl chloride or distannyl) is rapidly and quantitatively transformed into Sn-Li reagent at room temperature without formation of any (toxic) byproducts. The resulting Sn-Li reagent can be stored at ambient temperature for months and shows high reactivity toward various substrates, with quantitative atom efficiency.

Stille coupling via C–N bond cleavage

“…1 ). We started to examine the reaction of 1 with aryltrimethylstannane 2, which can be readily obtained by utilizing our recently developed naphthalene-catalysed quantitative synthesis of stannyl lithium 38 , or by employing functionalized Grignard reagents or other organometallics 39 . After the extensive experimentation ( Supplementary Tables 1–3 ), we identified the optimum conditions as heating a mixture of 1 (as triflate) and 2 in 1:1 ratio in dioxane with CsF as base, Ni(cod) 2 as catalyst and 1,3-dicyclohexylimidazol-2-ylidene (ICy) as ligand.…”

Stereospecific Palladium‐Catalyzed Acylation of Enantioenriched Alkylcarbastannatranes: A General Alternative to Asymmetric Enolate Reactions

“…This limitation impeded our ability to employ derivatives of 1 extensively in stereospecific reactions. To address this deficiency, we have developed a method to prepare highly enantioenriched alkylcarbastannatranes via the S N 2 reaction of lithium carbastannatrane [17] and enantioenriched secondary alkyl mesylates (Scheme 5). This process should significantly expand the accessibility of unactivated, enantioenriched alkyl-carbastannatranes for potential use in stereospecific reactions.…”

Stereospecific Palladium‐Catalyzed Acylation of Enantioenriched Alkylcarbastannatranes: A General Alternative to Asymmetric Enolate Reactions

“…This limitation impeded our ability to employ derivatives of 1 extensively in stereospecific reactions. To address this deficiency, we have developed a method to prepare highly enantioenriched alkylcarbastannatranes via the S N 2 reaction of lithium carbastannatrane and enantioenriched secondary alkyl mesylates (Scheme ). This process should significantly expand the accessibility of unactivated, enantioenriched alkylcarbastannatranes for potential use in stereospecific reactions.…”