Diversity-Oriented Approaches to Polycycles and Heterocycles via Enyne Metathesis and Diels–Alder Reaction as Key Steps

Kotha, Sambasivarao; Chavan, Arjun S.; Goyal, Bhupesh

doi:10.1021/acsomega.9b03020

Cited by 26 publications

(12 citation statements)

References 50 publications

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“…The substituted dihydropyrans 12 obtained by the RCEYM of oxaenediynes 2 contain both a triple bond and a conjugated diene system. We were interested in the possible orthogonal transformation of the products and hence carried out the Diels-Alder reaction of the dihydropyran 12b with N-phenylmaleimide (13) as described in [41]. The reaction at rt in dichloromethane gave the target product 14 in a moderate 45% isolated yield as a mixture of two diastereoisomers (Scheme 14).…”

Section: Diels-alder Reaction Of Rceym Product 12bmentioning

confidence: 99%

Ring-closing metathesis of prochiral oxaenediynes to racemic 4-alkenyl-2-alkynyl-3,6-dihydro-2H-pyrans

Kolaříková

Rybáčková

Svoboda

et al. 2020

Beilstein J. Org. Chem.

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The prochiral 4-(allyloxy)hepta-1,6-diynes, optionally modified in the positions 1 and 7 with an alkyl or ester group, undergo a chemoselective ring-closing enyne metathesis yielding racemic 4-alkenyl-2-alkynyl-3,6-dihydro-2H-pyrans. Among the catalysts tested, Grubbs 1st generation precatalyst in the presence of ethene (Mori conditions) gave superior results compared to the more stable Grubbs or Hoveyda–Grubbs 2nd generation precatalysts. This is probably caused by a suppression of the subsequent side-reactions of the enyne metathesis product with ethene. On the other hand, the 2nd generation precatalysts gave better yields in the absence of ethene. The metathesis products, containing both a triple bond and a conjugated system, can be successfully orthogonally modified. For example, the metathesis product of 5-(allyloxy)nona-2,7-diyne reacted chemo- and stereoselectively in a Diels–Alder reaction with N-phenylmaleimide affording the tricyclic products as a mixture of two separable diastereoisomers, the configuration of which was estimated by DFT computations. The reported enediyne metathesis paves the way to the enantioselective enyne metathesis yielding chiral building blocks for compounds with potential biological activity, e.g., norsalvinorin or cacospongionolide B.

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Section: Diels-alder Reaction Of Rceym Product 12bmentioning

confidence: 99%

Ring-closing metathesis of prochiral oxaenediynes to racemic 4-alkenyl-2-alkynyl-3,6-dihydro-2H-pyrans

Kolaříková

Rybáčková

Svoboda

et al. 2020

Beilstein J. Org. Chem.

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“…We were interested in their possible orthogonal transformations and hence carried out Diels-Alder reaction of dihydropyran 12b with N-phenylmaleimide (13) in analogy to Ref. [33]. The reaction at RT in dichloromethane gave the target product 14 in a moderate 45% isolated yield as a mixture of two diastereoisomers (Scheme 14).…”

Section: Diels-alder Reaction Of Rceym Product 12bmentioning

confidence: 99%

Ring closing metathesis of prochiral oxaenediynes to racemic 4-alkenyl-2-alkynyl-3,6-dihydro-2H-pyrans

Kolaříková¹,

Rybáčková²,

Svoboda³

et al. 2020

Preprint

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Prochiral 4-(allyloxy)hepta-1,6-diynes, optionally modified in the positions 1 and 7 with an alkyl or ester group, undergo chemoselective ring closing enyne metathesis yielding racemic 4-alkenyl-2-alkynyl-3,6-dihydro-2H-pyrans. Among the catalysts tested, Grubbs 1st generation precatalyst in the presence of ethene (Mori conditions) gave superior results compared to more stable Grubbs or Hoveyda-Grubbs 2nd generation precatalysts. This is probably caused by suppression of subsequent side-reactions of the enyne metathesis product with ethene. On the other hand, 2nd generation precatalysts gave better yields in the absence of ethene. The metathesis products, containing both triple bond and conjugated system, can be successfully orthogonally modified. For example, metathesis product of 5-(allyloxy)nona-2,7-diyne reacted chemo- and stereoselectively by Diels-Alder reaction with N-phenylmaleimide affording tricyclic products as the mixture of two separable diastereoisomers, the configuration of which was estimated by DFT computations. The reported enediyne metathesis paves the way to enantioselective enyne metathesis yielding chiral building blocks for compounds with potential biological activity, e.g. norsalvinorin or cacospongionolide B.

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“…In ingeniously elaborated procedures, olefin metathesis has been frequently employed as such or associated with name reactions like Grignard, Wittig, Diels-Alder, Suzuki-Miyaura, Heck, etc., resulting in the assembly of diverse intricate building blocks of the targeted structures [44]. Among the various embodiments of olefin metathesis, the highly chemoselective enyne metathesis reaction [45][46][47][48][49] has led to some of the most striking advances in the development of modern, efficient synthetic protocols [50,51]. Thus, the present account focuses on the impressive potential of enyne metathesis in providing sustainable access to bioactive organic compounds, when used in conjunction with a number of name reactions.…”

Section: Introductionmentioning

confidence: 99%

Combining enyne metathesis with long-established organic transformations: a powerful strategy for the sustainable synthesis of bioactive molecules

Drăguţan¹,

Drăguţan²,

Demonceau³

et al. 2020

Beilstein J. Org. Chem.

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This account surveys the current progress on the application of intra- and intermolecular enyne metathesis as main key steps in the synthesis of challenging structural motifs and stereochemistries found in bioactive compounds. Special emphasis is placed on ruthenium catalysts as promoters of enyne metathesis to build the desired 1,3-dienic units. The advantageous association of this approach with name reactions like Grignard, Wittig, Diels–Alder, Suzuki–Miyaura, Heck cross-coupling, etc. is illustrated. Examples unveil the generality of such tandem reactions in providing not only the intricate structures of known, in vivo effective substances but also for designing chemically modified analogs as valid alternatives for further therapeutic agents.

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Diversity-Oriented Approaches to Polycycles and Heterocycles via Enyne Metathesis and Diels–Alder Reaction as Key Steps

Cited by 26 publications

References 50 publications

Ring-closing metathesis of prochiral oxaenediynes to racemic 4-alkenyl-2-alkynyl-3,6-dihydro-2H-pyrans

Ring-closing metathesis of prochiral oxaenediynes to racemic 4-alkenyl-2-alkynyl-3,6-dihydro-2H-pyrans

Ring closing metathesis of prochiral oxaenediynes to racemic 4-alkenyl-2-alkynyl-3,6-dihydro-2H-pyrans

Combining enyne metathesis with long-established organic transformations: a powerful strategy for the sustainable synthesis of bioactive molecules

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