Lewis acid-assisted Ir(<scp>iii</scp>) reductive elimination enables construction of seven-membered-ring sulfoxides

Yang, Wu; Li, Yingzi; Zhu, Jiachen; Liu, Wentan; Ke, Jie; He, Chuan

doi:10.1039/d0sc04180g

Cited by 10 publications

(6 citation statements)

References 60 publications

(53 reference statements)

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“…Although the yield was decreased using this ligand, it can be increased by conducting the reaction at higher temperature without loss of ee. Addition of catalytic amount of Lewis acid further improved the yield, although the reason for this beneficial effect is not clear currently [16] …”

Section: Resultsmentioning

confidence: 97%

“…Addition of catalytic amount of Lewis acid further improved the yield, although the reason for this beneficial effect is not clear currently. [16] Next, we sought to identify suitable catalyst to reverse the regioselectivity. Ferrocene based ligand PPF-Cy (L11) and CyPF-Cy (L12) were not effective in the catalytic hydroalkynylation.…”

Section: Reaction Development Of Regiodivergent Hydroalkynylationmentioning

confidence: 99%

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Iridium‐Catalyzed Regiodivergent and Enantioselective Hydroalkynylation of Unactivated 1,1‐Disubstituted Alkenes

Wang

2022

Angew Chem Int Ed

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Catalytic enantioselective functionalization of unactivated 1,1‐disubstituted alkenes is challenging due to the difficulty to discriminate the enantiotopic faces. Enantioselective hydrofunctionalization of unactivated 1,1‐disubstituted alkenes with tunable Markovnikov and anti‐Markovnikov selectivity remains elusive. We report here an amide‐directed, regiodivergent and enantioselective hydroalkynylation of unactivated alkenes. The regioselectivity can be readily tuned by the choice of a proper ligand. Catalytic alkynylations occurred with tunable Markovnikov and anti‐Markovnikov selectivity to afford products containing acyclic tertiary or quaternary stereocenters β to an amide. Combining a sequence of alkene isomerization and regioselective hydroalkynylation, we further realized an iridium‐catalyzed formal asymmetric conjugated alkynylation of β,β‐disubstituted α,β‐unsaturated amides. Computational studies suggest that the regioselectivity is dictated by the ligand structures.

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Section: Resultsmentioning

confidence: 97%

Section: Reaction Development Of Regiodivergent Hydroalkynylationmentioning

confidence: 99%

Iridium‐Catalyzed Regiodivergent and Enantioselective Hydroalkynylation of Unactivated 1,1‐Disubstituted Alkenes

Wang

2022

Angew Chem Int Ed

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“…Beside Pd‐catalyzed reactions, He and co‐workers unlocked the use of Ir III complexes for the sulfinyl directed C−H activation. Optimizing their previous conditions for the C−H amidation of aryl sulfoxides, [28] they achieved the intramolecular coupling of dibenzyl sulfoxides through a double C−H activation (Scheme 5.d) [29] . To obtain the desired seven‐membered thiepine S ‐oxide, the reductive elimination step needed to be promoted by the addition of a Lewis acid such as silver salts.…”

Section: Intramolecular Cyclization Via Sulfoxide‐directed C−h Activa...mentioning

confidence: 99%

“… Intramolecular cyclization involving sulfoxide‐directed single or double C−H activation of arenes [25–27,29] …”

Section: Intramolecular Cyclization Via Sulfoxide‐directed C−h Activa...mentioning

confidence: 99%

“…Intramolecular cyclization involving sulfoxide-directed single or double CÀ H activation of arenes. [25][26][27]29] Antonchick's conditions allowed a double CÀ H oxidative cyclization leading to sulfoxide-bridged polycycles (Scheme 5.c, n = 0). [27] Moreover, the method could be extended to the preparation of six-and seven-membered rings from benzyl or arylethyl sulfoxides, respectively, avoiding the abovementioned Pummerer cascade rearrangement (Scheme 5.c, n = 1,2).…”

Section: Intramolecular Cyclization Via Sulfoxide-directed Cà H Activ...mentioning

confidence: 99%

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Aryl Sulfoxides: A Traceless Directing Group for Catalytic C−H Activation of Arenes

Marqués,

Kammerer

2024

ChemPlusChem

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The transition‐metal catalyzed C‐H activation of arenes directed by sulfoxides represents a compelling strategy in organic synthesis, owing to its exceptional regioselectivity and high efficiency. This innovative approach stands out for its traceless character, enabling the direct functionalization of arenes, before the easy removal or conversion of the key sulfinyl moiety. Beyond their utility as a directing group, sulfoxides have proved particularly valuable to mediate as chiral auxiliaries, presenting exciting prospects for the synthesis of stereo‐enriched compounds upon C‐H functionalization. The versatility demonstrated by the method paves the way to different structures with potential applications ranging from medicinal chemistry to organic electronic.

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Iridium‐Catalyzed Regiodivergent and Enantioselective Hydroalkynylation of Unactivated 1,1‐Disubstituted Alkenes

Wang

2022

Angewandte Chemie

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Catalytic enantioselective functionalization of unactivated 1,1-disubstituted alkenes is challenging due to the difficulty to discriminate the enantiotopic faces. Enantioselective hydrofunctionalization of unactivated 1,1-disubstituted alkenes with tunable Markovnikov and anti-Markovnikov selectivity remains elusive. We report here an amide-directed, regiodivergent and enantioselective hydroalkynylation of unactivated alkenes. The regioselectivity can be readily tuned by the choice of a proper ligand. Catalytic alkynylations occurred with tunable Markovnikov and anti-Markovnikov selectivity to afford products containing acyclic tertiary or quaternary stereocenters β to an amide. Combining a sequence of alkene isomerization and regioselective hydroalkynylation, we further realized an iridium-catalyzed formal asymmetric conjugated alkynylation of β,β-disubstituted α,β-unsaturated amides. Computational studies suggest that the regioselectivity is dictated by the ligand structures.

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Lewis acid-assisted Ir(iii) reductive elimination enables construction of seven-membered-ring sulfoxides

Abstract: Iridium has played an important role in the evolution of C−H activation chemistry over the last half century owing to its high reactivity towards stoichiometric C–H bond cleavage, however, the...

Cited by 10 publications

References 60 publications

Iridium‐Catalyzed Regiodivergent and Enantioselective Hydroalkynylation of Unactivated 1,1‐Disubstituted Alkenes

Iridium‐Catalyzed Regiodivergent and Enantioselective Hydroalkynylation of Unactivated 1,1‐Disubstituted Alkenes

Aryl Sulfoxides: A Traceless Directing Group for Catalytic C−H Activation of Arenes

Iridium‐Catalyzed Regiodivergent and Enantioselective Hydroalkynylation of Unactivated 1,1‐Disubstituted Alkenes

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