Anionic Cross‐Coupling Reaction of α‐Metallated Alkenyl Sulfoximines and Alkenyl Sulfoximines with Cuprates Featuring a 1,2‐Metal‐Ate Rearrangement of Sulfoximine‐Substituted Higher Order Alkenyl Cuprates and an α‐Metallation of Alkenyl Sulfoximines by Cuprates

Gais, Hans‐Joachim; Rao, Changqing; Loo, Ralf

doi:10.1002/chem.200800455

Cited by 25 publications

(16 citation statements)

References 65 publications

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“…A pre-complex between the cuprate base and the sulfoximine group was proposed as a possible explanation for the reaction. 55 However, with the exception of this study, other examples reported in the literature concerning deprotometallation using cuprate bases have involved aromatic substrates. Moreover, it is noteworthy that these studies have focused on Lipshutz cuprates and, as defined in section 2 of this review, Lipshutz-type cuprates.…”

Section: Gilman Cuprates and Structural Interconversionmentioning

confidence: 68%

New avenues in the directed deprotometallation of aromatics: recent advances in directed cupration

et al. 2014

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Recent advances in the selective deprotometallation of aromatic reagents using alkali metal cuprates are reported. The ability of these synergic bases to effect deprotonation under the influence of a directing group is explored in the context of achieving new and more efficient organic transformations whilst encouraging greater ancillary group tolerance by the base. Developments in our understanding of the structural chemistry of alkali metal cuprates are reported, with both Gilman cuprates of the type R2CuLi and Lipshutz and related cuprates of the type R2Cu(X)Li2 (X = inorganic anion) elucidated and rationalised in terms of ligand sterics. The generation of new types of cuprate motif are introduced through the development of adducts between different classes of cuprate. The use of DFT methods to interrogate the mechanistic pathways towards deprotonative metallation is described. Theoretical modelling of in situ rearrangements undergone by the cuprate base are discussed, with a view to understanding the relationship between R2CuLi and R2Cu(X)Li2, their interconversion and the implications of this for cuprate reactivity. The advent of a new class of adduct between different cuprate types is developed and interpreted in terms of the options for expelling LiX from R2Cu(X)Li2. Applications in the field of medicinal chemistry and (hetero)arene derivatization are explored.

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Section: Gilman Cuprates and Structural Interconversionmentioning

confidence: 68%

New avenues in the directed deprotometallation of aromatics: recent advances in directed cupration

et al. 2014

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“…We had previously studied the RCDEM of trienes of type XIV (R 1 = alkenyl, Scheme ), which gave the corresponding medium‐sized carbocycles 14b. Alkenylsulfoximines XV are readily lithiated at the α‐position at low temperatures, with formation of the corresponding Z ‐configured α‐lithioalkenylsulfoximines 12e,12g,15b. At 0 °C they undergo isomerization to the corresponding E ‐configured α‐lithioalkenylsulfoximines, which can be trapped by unsaturated aldehydes to give the allylic alcohols XIV (R 1 = alkenyl) 14b.…”

Section: Resultsmentioning

confidence: 99%

Spiro‐ and Bicycloannulation of Sulfoximine‐Substituted 2‐Hydroxy‐dihydropyrans: Enantioselective Synthesis of Spiroketals, Spiroethers, and Oxabicycles and Structure of Dihydropyran Oxocarbenium Ions

et al. 2013

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A modular enantioselective synthesis of spiroketals, spiroethers, and oxabicycles, each containing a dihydropyran subunit, is described. It is based on the 2,2‐spiro‐ and 2,6‐bicycloannulation of sulfoximine‐substituted 2‐hydroxy‐dihydropyrans. Key steps of the spiroannulations are the ring‐closing metathesis of the corresponding 2,2‐oxadienyl and 2,6‐dienyl dihydropyrans and Prins cyclization of 2‐alkenyl 2‐hydroxy‐dihydropyrans. Ring‐closing metathesis of the corresponding 2,6‐dienyl dihydropyrans gave oxabicycles with oxabicyclo[4.3.1]decane skeletons. These routes were extended to the synthesis of spiroketals and spiroethers incorporating additional annulated six‐membered rings. Diastereoselective Prins cyclization of mono‐ and bicyclic 2‐alkenyl‐2‐hydroxy‐dihydropyrans was highly selective and afforded chloro‐substituted spirocycles. Substituted 2‐hydroxy‐dihydropyrans were obtained through cyclization of δ‐hydroxy ketones, which were synthesized from enantiomerically pure sulfoximine‐substituted homoallylic alcohols through lithiation and trapping of the α‐lithioalkenylsulfoximines with unsaturated aldehydes, followed by allylic oxidation. Inter‐ and intramolecular glycosidations of the 2‐hydroxy‐dihydropyrans with O‐ and C‐nucleophiles proceeded with high stereoselectivities and furnished 2,6‐trans‐configured glycosides. Dihydropyran oxocarbenium ions are most likely intermediates in the glycosidations. According to ab initio calculations, sulfoximine‐ and trimethyl‐substituted dihydropyran oxocarbenium ions adopt a half‐chair‐like conformation. The energy difference between the oxocarbenium ion with pseudoaxial and the one with pseudoequatorial methyl groups is very small. A transition state model for their reactions with nucleophiles is proposed. It features a half‐chair‐like conformation, a pseudoequatorial C6 substituent, and an anti‐addition of the nucleophile along an axial trajectory to C2 that produces an anti‐periplanar lone pair at the O atom. A similar transition state model allows a general explanation for the trans stereoselectivity of the reactions between C6‐substituted dihydropyran oxocarbenium ions and nucleophiles.

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“…On the one hand, it stabilizes the electron‐rich metal center in the Ni 0 ‐intermediates and on the other hand it participates in controlling the reaction barriers that lead to the key Ni 0 ‐vinylidene and dianionic Ni 0 ‐ate intermediates of the ACCR pathways. The mechanism of the Ni catalyzed ACCR of lithioalkenyl sulfoximines is distinctly different from that of the Cu catalyzed ACCR of lithioalkenyl ethers and Cu mediated ACCR of litthioalkenyl sulfoximines, which has been postulated as key step a 1,2‐metalate shift of higher‐order cuprates under displacement of the nucleofuge at the sp 2 C atom.…”

Section: Discussionmentioning

confidence: 99%

Nickel‐Catalyzed Anionic Cross‐Coupling Reaction of Lithium Sulfonimidoyl Alkylidene Carbenoids With Organolithiums

Erdelmeier

Won

Park

et al. 2020

Chemistry A European J

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The mechanistic platform for a novel nickel0‐catalyzed anionic cross‐coupling reaction (ACCR) of lithium sulfonimidoyl alkylidene carbenoids (metalloalkenyl sulfoximines) with organometallic reagents is reported herein, affording substituted alkenylmetals and lithium sulfinamides. The Ni0‐catalyzed ACCR of three different types of metalloalkenyl sulfoximines, including acyclic, axially chiral and exocyclic derivatives, with sp2 organolithiums and sp2 and sp3 Grignard reagents has been studied. The ACCR of metalloalkenyl sulfoximines with PhLi in the presence of the Ni0‐catalyst and precatalyst Ni(PPh3)2Cl2 afforded alkenyllithiums, under inversion of configuration at the C atom and complete retention at the S atom. In a combination of experimental and DFT studies, we propose a catalytic cycle of the Ni0‐catalyzed ACCR of lithioalkenyl sulfoximines. Computational studies reveal two distinctive pathways of the ACCR, depending on whether a phosphine or 1,5‐cyclooctadiene (COD) is the ligand of the Ni atom. They rectify the underlying importance of forming the key Ni0‐vinylidene intermediate through an indispensable electron‐rich Ni0‐center coordinated by phosphine ligands. Fundamentally, we present a mechanistic study in controlling the diastereoselectivity of the alkenyllithium formation via the key lithium sulfinamide coordinated Ni0‐vinylidene complex, which consequently avoids an unselective formation of an alkylidene carbene Ni‐complex and ultimately racemic alkenyllithium.

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Anionic Cross‐Coupling Reaction of α‐Metallated Alkenyl Sulfoximines and Alkenyl Sulfoximines with Cuprates Featuring a 1,2‐Metal‐Ate Rearrangement of Sulfoximine‐Substituted Higher Order Alkenyl Cuprates and an α‐Metallation of Alkenyl Sulfoximines by Cuprates

Cited by 25 publications

References 65 publications

New avenues in the directed deprotometallation of aromatics: recent advances in directed cupration

New avenues in the directed deprotometallation of aromatics: recent advances in directed cupration

Spiro‐ and Bicycloannulation of Sulfoximine‐Substituted 2‐Hydroxy‐dihydropyrans: Enantioselective Synthesis of Spiroketals, Spiroethers, and Oxabicycles and Structure of Dihydropyran Oxocarbenium Ions

Nickel‐Catalyzed Anionic Cross‐Coupling Reaction of Lithium Sulfonimidoyl Alkylidene Carbenoids With Organolithiums

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