Titanocene‐Catalyzed Radical Opening of N‐Acylated Aziridines

Zhang, Yongqiang; Vogelsang, Elisabeth; Qu, Zheng‐Wang; Gansäuer, Andreas

doi:10.1002/ange.201707673

Cited by 26 publications

(4 citation statements)

References 61 publications

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“…Combining the above approaches, both Gansauer and Lin have each demonstrated that three-membered ring rupture can also be promoted by a-carbonyl reduction in N-acyl aziridines 279,280 and cyclopropylketones 281 (FIG. 6c).…”

Section: Catalytic Single-electron Transfermentioning

confidence: 99%

Modern applications of low-valent early transition metals in synthesis and catalysis

et al. 2018

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Low-valent early transition metals are often intrinsically highly reactive as a result of their strong propensity toward oxidation to more stable high-valent states. Harnessing these highly reducing complexes for productive reactivity is potentially powerful for C-C bond construction, organic reductions, small-molecule activation and many other reactions that offer orthogonal chemoselectivity and/or regioselectivity patterns to processes promoted by late transition metals. Recent years have seen many exciting new applications of low-valent metals through building new catalytic and/or multicomponent reaction manifolds out of classical reactivity patterns. In this Review, we survey new methods that employ early transition metals and invoke low-valent precursors or intermediates in order to identify common themes and strategies in synthesis and catalysis.

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Section: Catalytic Single-electron Transfermentioning

confidence: 99%

Modern applications of low-valent early transition metals in synthesis and catalysis

et al. 2018

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“…In 2017, Gansaüer expanded the scope of titanocene-based reactivity from epoxides to N-acylaziridines, achieving their reductive ring opening followed by Giese-type addition to electron-deficient alkenes (Scheme 8). 52 For example, aziridine 61a can be activated by Cp* 2 Ti III Cl through Ti−carbonyl coordination (63) and subsequent SET, resulting in ring rupture and formation of radical intermediate 64. This intermediate then adds to acrylate 23, leading to adduct 65 after further reduction by Ti III .…”

Section: Introductionmentioning

confidence: 99%

Recent Advances in Titanium Radical Redox Catalysis

2019

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New catalytic strategies that leverage single-electron redox events have provided chemists with useful tools for solving synthetic problems. In this context, Ti offers opportunities that are complementary to late transition metals for reaction discovery. Following foundational work on epoxide reductive functionalization, recent methodological advances have significantly expanded the repertoire of Ti radical chemistry. This Synopsis summarizes recent developments in the burgeoning area of Ti radical catalysis with a focus on innovative catalytic strategies such as radical redox-relay and dual catalysis.

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“…The challenge of realizing electrophilic ring-opening reactions lies in overturning the intrinsic electrophilic nature of ring molecules. To date, the most successful examples of catalytic electrophilic ring-opening reactions are limited to epoxides [2][3][4][5][6][7][8][9][10][11][12][13][14] with a few exceptions of other small, strained rings, such as aziridines, [15][16][17][18][19] oxetanes, 20 azetidinones, 21,22 cyclobutanones, 23 and cyclobutanone oxime esters. 24 Therefore, it is highly desirable to develop a new methodology to allow electrophilic ring-opening reactions to go beyond the small ring system.…”

Section: Introductionmentioning

confidence: 99%

Nickel-Catalyzed Reductive Electrophilic Ring-Opening of Benzofurans with Alkyl Halides

2022

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In this paper, we developed an electrophilic ring-opening reaction, which is beyond the strained small ring system. Under reductive nickel catalysis, ring-opening of diverse benzofurans via endocyclic inert carbon-oxygen bond cleavage can be achieved with an array of inactivated secondary and tertiary alkyl halides as coupling partners, allowing for the preparation of a series of (E)-o-alkenylphenols with excellent E/Z-selectivity and high functional tolerance. The utility of this method was further demonstrated through derivatizations of the ring-opening products using the o-hydroxyl group as a functional

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Titanocene‐Catalyzed Radical Opening of N‐Acylated Aziridines

Cited by 26 publications

References 61 publications

Modern applications of low-valent early transition metals in synthesis and catalysis

Modern applications of low-valent early transition metals in synthesis and catalysis

Recent Advances in Titanium Radical Redox Catalysis

Nickel-Catalyzed Reductive Electrophilic Ring-Opening of Benzofurans with Alkyl Halides

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