On the Macrocyclization of the Erythromycin Core: Preorganization is Not Required

Stang, Erik M.; White, M. Christina

doi:10.1002/anie.201007309

Cited by 63 publications

(16 citation statements)

References 43 publications

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“…Earlier Pd-catalyzed macrolactonization methods required a stoichiometric amount of an external oxidant. 83 In 2012, the Breit group developed an atom-economical intramolecular macrolactonization of -alkynoic acids without an external oxidant, where 5-23-membered vinylic lactones were synthesized using the catalytic Rh(I)/DPEphos system (Scheme 64). 84 Due to formation of 'head-to-tail' dimerized side product, the yield decreased in the case of medium-sized rings.…”

Section: Using Oxygen Nucleophilesmentioning

confidence: 99%

Rhodium-Catalyzed Allylation Reactions

Thoke

Kang

2019

Synthesis

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Rhodium-catalyzed allylation reactions are well known for their unique selectivity and reactivity due to the high memory effect of Rh as compared to other metals. These reactions involve the substitution of allylic rhodium intermediates with a diverse range of different nucleophiles, leading to C–C and C–heteroatom bond formation. Modern organic chemists are, however, interested in atom-economical protocols under greener pathways and following recent increased understanding of mechanistic aspects of Rh-catalyzed allylation via the hydrofunctionalization of allenes or alkynes, great strides have made in the design and development of new atom-economical protocols. In this article, we review this field from its beginning to current state.1 Introduction2 Rhodium-Catalyzed Allylic Substitution3 Rhodium-Catalyzed Allylation with Allenes4 Rhodium-Catalyzed Allylation with Alkynes5 Rhodium-Catalyzed Allylation with Dienes6 Rhodium-Catalyzed Allylation by ARO of Oxabicyclic Alkenes7 Rhodium-Catalyzed Enantioselective Allylation in Natural Product and Drug Synthesis8 Conclusion

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Section: Using Oxygen Nucleophilesmentioning

confidence: 99%

Rhodium-Catalyzed Allylation Reactions

Thoke

Kang

2019

Synthesis

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“…Compound 84 was characterized and appeared as a single product ( 1 H-NMR evidence); however, no further studies were performed to assign the stereochemistry of the newly formed stereocenter. With the aim to achieve high regio- and diastereo-selectivity, the authors hydrolyzed ester 83 to the corresponding carboxylic acid 86, which was then submitted to intramolecular lactonization via C-H allylic activation using White’s catalyst [ 62 , 63 , 64 ]. After a brief optimization, the authors found that the reaction of 86 with White’s catalyst in the presence of DDQ and Cr(III)salenCl gave lactone 87 as a single diastereoisomer in 40% yield with 50% recovery of the starting material.…”

Section: Resultsmentioning

confidence: 99%

The Therapeutic Potential of Migrastatin-Core Analogs for the Treatment of Metastatic Cancer

Giralt

2017

Molecules

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Tumor metastasis is a complex process in which cells detach from the primary tumor and colonize a distant organ. Metastasis is also the main process responsible for cancer-related death. Despite the enormous efforts made to unravel the metastatic process, there is no effective therapy, and patients with metastatic tumors have poor prognosis. In this regard, there is an urgent need for new therapeutic tools for the treatment of this disease. Small molecules with the capacity to reduce cell migration could be used to treat metastasis. Migrastatin-core analogs are naturally inspired macrocycles that inhibit pathological cell migration and are able to reduce metastasis in animal models. Migrastatin analogs can be synthesized from a common advanced intermediate. Herein we present a review of the synthetic approaches that can be used to prepare this key intermediate, together with a review of the biological activity of migrastatin-core analogs and current hypotheses concerning their mechanism of action.

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“…In 2011, they extended this methodology to the total synthesis of an erythromycin precursor, 6-deoxyerythronolide B (6-dEB). 57 3.1.1. Regioselective C(sp 3 )-H activation.…”

Section: C(sp 3 )-H Activation Reactions Of Carboxylic Acidsmentioning

confidence: 99%