Transition-metal-catalyzed C–H allylation reactions

Dutta, Subhabrata; Bhattacharya, Trisha; Werz, Daniel B.; Maiti, Debabrata

doi:10.1016/j.chempr.2020.10.020

Cited by 128 publications

(65 citation statements)

References 168 publications

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“…Transition-metal-catalyzed allylic substitution reactions are of significant utility in organic synthesis. [6][7][8][9][10][11] Various nucleophiles have been reported to undergo regioand enantio-selective allylic alkylation, providing access to a wide range of valuable chiral building blocks. However, the use of alkynyl nucleophiles in allylic substitution has remained underdeveloped, even though the 1,4-enyne structure that is accessible from this transformation is a versatile synthon in chemical synthesis.…”

Section: The Bigger Picturementioning

confidence: 99%

Ligand coordination- and dissociation-induced divergent allylic alkylations using alkynes

Huang

Liu

et al. 2021

Chem

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Section: The Bigger Picturementioning

confidence: 99%

Ligand coordination- and dissociation-induced divergent allylic alkylations using alkynes

Huang

Liu

et al. 2021

Chem

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“…Fundamental research on this valuable C-C bond formation was performed early on and led to the development of a variety of allylic organometallic reagents, 4 utilizing (semi)metals such as Zn, In, B, Sn, Mn, Sb, Mg, Bi, Cr or Al. 5 Later, focus predominantly switched towards the development of catalytic methods, 6 avoiding the (over)stoichiometric use of these often toxic and/or expensive reagents while significantly facilitating access to enantioenriched products. As a result, especially the catalytic use of chiral metal complexes became state of the art as a convenient method to exert stereocontrol in allylation reactions.…”

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confidence: 99%

Asymmetric Addition of Allylsilanes to Aldehydes – A Cr/Photoredox Dual Catalytic Approach Complementing the Hosomi–Sakurai Reaction

Schäfers

Dutta

Kleinmans

et al. 2021

Preprint

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The allylation of aldehydes is a fundamental transformation in synthetic organic chemistry. Among the multitude of available reagents, especially allylsilanes have been established as preferred allyl source. As initially reported by Hosomi & Sakurai, these non-toxic and highly stable reagents add to carbonyls via an open transition state upon Lewis acid activation. Herein, we report a general strategy to access a variety of valuable homoallylic alcohols in opposite chemo- and diastereoselectivity to the established Hosomi–Sakurai conditions by switching to photocatalytic activation in combination with a closed transition state (Chromium catalysis). Moreover, this dual catalytic approach displays a straightforward way to introduce excellent levels of enantioselectivity and its mild conditions allow for a broad substrate scope including chiral boron-substituted products as a highlight. To emphasize the synthetic utility, our method was applied as the key step in the synthesis of a bioactive compound and in the late-stage functionalization of steroid derivatives. Detailed mechanistic studies and DFT calculations hint towards an unprecedented photo-initiated chain being operative.

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“…Since the reactivity and the regioselectivity can be affected by the structure of both benzyl electrophiles and nucleophiles, the exploration of such new reaction partners would be beneficial to expand their synthetic utilities. Herein, we report a highly regioselective aromatic C–H allylation of N -(arylmethyl)sulfonimides with allyl Grignard reagents involving palladium-catalyzed benzylic C–N cleavage (Scheme b) …”

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confidence: 99%

Highly Regioselective Aromatic C–H Allylation of N-(Arylmethyl)sulfonimides with Allyl Grignard Reagents Involving Benzylic C–N Cleavage

2021

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A new pair of reaction partners has been established for the aromatic C−H functionalization of benzyl electrophiles with nucleophiles via palladium-catalyzed benzylic C−N cleavage. A range of N-(1-naphthylmethyl)sulfonimides, N-(2-thienylmethyl)sulfonimides, and N-(2-furanylmethyl)sulfonimides smoothly underwent palladium-catalyzed aromatic C−H allylation with allyl Grignard reagents at room temperature, delivering structurally diverse substituted 1-allylnaphthalenes and 2-allylheteroarenes in moderate to excellent yields with extremely high regioselectivities. Replacing the N-(arylmethyl)sulfonimide with an (arylmethyl)ammonium salt, an arylmethyl chloride, or an arylmethyl phosphate as the benzyl electrophile leads to a dramatic erosion of the regioselectivity.

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Transition-metal-catalyzed C–H allylation reactions

Cited by 128 publications

References 168 publications

Ligand coordination- and dissociation-induced divergent allylic alkylations using alkynes

Ligand coordination- and dissociation-induced divergent allylic alkylations using alkynes

Asymmetric Addition of Allylsilanes to Aldehydes – A Cr/Photoredox Dual Catalytic Approach Complementing the Hosomi–Sakurai Reaction

Highly Regioselective Aromatic C–H Allylation of N-(Arylmethyl)sulfonimides with Allyl Grignard Reagents Involving Benzylic C–N Cleavage

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