Two New Modes of Pd-Catalyzed Domino-Tetracyclization of Bromodienynes—5-exo-trig Cyclization Wins overβ-Hydride Elimination

Schweizer, Stefan; Song, Zhi Zhong; Meyer, Frank; Parsons, Philip J.; Meijere, Armin de

doi:10.1002/(sici)1521-3773(19990517)38:10<1452::aid-anie1452>3.0.co;2-p

Cited by 67 publications

(22 citation statements)

References 2 publications

(4 reference statements)

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“…The Mizoroki‐Heck reaction has played a pivotal role in the synthesis of an immense array of industrially and pharmaceutically important compounds . Mechanistically, the Heck reaction proceeds through the formation of an alkyl‐Pd complex and subsequent β‐hydride elimination which is the key step in determining the selectivity between Mizoroki‐Heck product vs 1,4‐addition product (known as reductive Heck product), tuned by presence/absence of the external hydride source . In 1980s, Cacchi et al .…”

Section: Introductionmentioning

confidence: 99%

Palladium Nanoparticles‐Catalyzed Synthesis of Indanone Derivatives via Intramolecular Reductive Heck Reaction

Parveen

Sekar

2019

Adv Synth Catal

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An efficient protocol for the straightforward, single-step synthesis of 3-aryl-1-indanones from 2'iodochalcone via reductive Heck reaction using phosphine free, stable and reusable binaphthyl stabilized palladium nanoparticle (Pd-BNP) as a catalyst has been described. An immense array of substrate scope with electron-rich and deficient 2'-iodochalcones have been synthesized. Further derivatization of product indanones have been achieved successfully. The heterogeneous nature of the Pd-BNP has been validated by centrifugation test and mercury poisoning experiment. Pd-BNP has been successfully recycled up to 5 cycles without any significant loss in reaction yield and particle size of nanoparticles, confirmed by TEM analysis. 3-(4-(Trifluoromethyl)phenyl)-2,3-dihydro-1H-inden-1-one(2 r): 78% yield (53.8 mg); Yellow liquid; R f 0.53 (10% ethyl acetate in hexanes); 1 H NMR (400 MHz, CDCl 3 ): δ 2.66 (dd, cm À 1 ; HRMS (m/z): [M + Na] + calcd for C 16 H 11 OF 3 Na: 299.0660; found: 299.0651. 3-(3-Nitrophenyl)-2,3-dihydro-1H-inden-1-one (2 s): 70% yield (44.3 mg); Greenish solid; mp 125°C; R f 0.42 (20% ethyl acetate in hexanes); 1 H NMR (400 MHz, CDCl 3 ): δ 2.66 (dd,

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Section: Introductionmentioning

confidence: 99%

Palladium Nanoparticles‐Catalyzed Synthesis of Indanone Derivatives via Intramolecular Reductive Heck Reaction

Parveen

Sekar

2019

Adv Synth Catal

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“…Oh et al [99] and de Meijere and Co-workers [100] reported palladium-catalyzed cyclization reactions in which cyclizations are preferred over the b-elimination routes.…”

Section: Other Methods Of Suppressing the B-hydride Eliminationmentioning

confidence: 99%

Control of the β-Hydride Elimination Making Palladium-Catalyzed Coupling Reactions more Diversified

2005

Top Catal

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“…The reaction required 2,2‐disubstituted terminal olefins so that in situ‐generated C(sp 3 )‐PdX species would contain no β‐H. A similar Pd‐catalyzed cascade cyclization was also reported by de Meijere and coworkers in which four 6/5/6/3‐membered rings were generated sequentially in one step (Scheme ) …”

Section: Dicarbofunctionalization Of Tethered Olefins Involving Cyclimentioning

confidence: 99%

Transition Metal‐Catalyzed Dicarbofunctionalization of Unactivated Olefins

Dhungana

Basnet

et al. 2018

The Chemical Record

383

116

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Transition metal (TM)-catalyzed difunctionalization of unactivated olefins with two carbon-based entities is a powerful method to construct complex molecular architectures rapidly from simple and readily available feedstock chemicals. While dicarbofunctionalization of unactivated olefins has a long history typically with the use of either carbon monoxide to intercept C(sp )-[M] (alkyl-TM) species or substrates lacking in β-hydrogen (β-Hs), development of this class of reaction still remains seriously limited due to complications of β-H elimination arising from the in situ-generated C(sp )-[M] intermediates. Over the years, different approaches have been harnessed to suppress β-H elimination, which have led to the development of various types of olefin dicarbofunctionalization reactions even in substrates that generate C(sp )-[M] intermediates bearing β-Hs with a wide range of electrophiles and nucleophiles. In this review, these developments will be discussed both through the lens of historical perspectives as well as the strategies scrutinized over the years to address the issue of β-H elimination. However, this review article by no means is designed to be exhaustive in the field, and is merely presented to provide the readers an overview of the key reaction developments.

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Two New Modes of Pd-Catalyzed Domino-Tetracyclization of Bromodienynes—5-exo-trig Cyclization Wins overβ-Hydride Elimination

Abstract: Remarkable increases of molecular complexity in a single procedural step are achieved with the title reaction. Only a slight modification in the substitution pattern on the acyclic precursor 2 can change the mode of tetracyclization to either yield skeletons of type 1 or 3 exclusively.

Cited by 67 publications

References 2 publications

Palladium Nanoparticles‐Catalyzed Synthesis of Indanone Derivatives via Intramolecular Reductive Heck Reaction

Palladium Nanoparticles‐Catalyzed Synthesis of Indanone Derivatives via Intramolecular Reductive Heck Reaction

Control of the β-Hydride Elimination Making Palladium-Catalyzed Coupling Reactions more Diversified

Transition Metal‐Catalyzed Dicarbofunctionalization of Unactivated Olefins

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