Synthesis of unexpected nitrogen heterocycles via Pd-catalyzed cross-coupling of o-isopropenyl and methallyl anilides with vinylic halides

Larock, Richard C.; Pace, Paola; Yang, Hoseok

doi:10.1016/s0040-4039(98)00383-9

Cited by 28 publications

(2 citation statements)

References 3 publications

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“…In a BF 3 -mediated condensation–cyclization cascade, diene 2a was converted to N -arylindole 5 with p -benzoquinone in 70% yield. Mesylation of compound 2a gave sulfonamide 6 in 92% yield, which was further cyclized with BF 3 under mild conditions to obtain indoline rac - 7 in 67% yield with good trans diastereoselectivity . Mild and selective N -alkynylation of mesylamide 6 was achieved using TIPS-EBX ( 9 ) as the alkyne-transfer reagent.…”

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confidence: 99%

NH₂-Directed C–H Alkenylation of 2-Vinylanilines with Vinylbenziodoxolones

2017

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The first directing-group-mediated C-H alkenylation with alkenyl-λ-iodanes as electrophilic alkene-transfer reagents has been developed. The application of free aromatic amines as challenging but synthetically valuable directing groups in combination with an Ir catalyst enabled the synthesis of highly desirable 1,3-dienes in excellent yields of up to 98% with high to perfect (Z,E) stereoselectivity. A broad substrate scope and further synthetic modifications are demonstrated.

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confidence: 99%

NH₂-Directed C–H Alkenylation of 2-Vinylanilines with Vinylbenziodoxolones

2017

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“…The preparation of heterocyclic compounds based on the intramolecular nucleophilic attack on η 3 -allylpalladium complexes derived from olefins containing proximate nucleophiles and vinylic triflates or halides is evolving as an efficient and versatile synthetic methodology (Scheme 1). A variety of oxygen 1 and nitrogen 2,3 heterocycles have been obtained according to this protocol.…”

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Synthesis of Dihydropyrans via Pd-Catalyzed Cyclization of 2-Allyl-1,3-dicarbonyl Compounds and Vinylic Triflates or Halides

Cacchi¹,

Fabrizi²,

Larock³

et al. 1998

Synlett

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The palladium-catalyzed reaction of 2-allyl-1,3-dicarbonyl compounds with vinylic triflates or halides affords dihydropyran derivatives, most probably through the intermediacy of η 3 -allylpalladium complexes that undergo an intramolecular nucleophilic attack by the oxygen.The preparation of heterocyclic compounds based on the intramolecular nucleophilic attack on η 3 -allylpalladium complexes derived from olefins containing proximate nucleophiles and vinylic triflates or halides is evolving as an efficient and versatile synthetic methodology (Scheme 1). A variety of oxygen 1 and nitrogen 2,3 heterocycles have been obtained according to this protocol. Scheme 1As a further extension of this chemistry, we now report our preliminary results on the utilization of readily available 2-allyl-1,3-dicarbonyl compounds 1 4 as convenient building blocks for the preparation of the substituted dihydropyrans 3 (Scheme 2). Scheme 2Prior experience has shown that the nature of the nucleophile in these reactions can be of considerable importance in controlling the ratio of cyclization to vinylic substitution (see Scheme 4). Stronger, anionic nucleophiles appear to favor the cyclization path. 2 Therefore, the reaction of ethyl 2-allyl-3-oxobutanoate with 17β-acetoxyandrosta-3,5-dienyl-3-yl triflate (Scheme 3), our model system, was initially investigated in the presence of a variety of bases. The presence of additives has also been found to play a key role. Some of our results are summarized in Table 1.

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