Enantioconvergent Formal Synthesis of Brefeldin A via Sakai-Catalyzed Cyclization

Ducray, Pierre; Rousseau, Bernard; Mioskowski, Charles

doi:10.1021/jo990507w

Cited by 25 publications

(15 citation statements)

References 29 publications

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“…The two earliest parallel kinetic resolution methodologies proceed via an intramolecular hydroacylation reaction (Scheme ). In 1999, Rousseau, Mioskowski, and their co-worker reported a stereodivergent resolution as part of an enantioconvergent formal synthesis of bredfeldin A . Silyl-protected alcohol 554 was treated with [Rh( S )-BINAP]BF 4 , producing the two diastereomeric cyclopentanones cis - 555 and trans - 555 in a 1:1 ratio and both in 96% ee.…”

Section: Kinetic Resolutionsmentioning

confidence: 99%

Catalytic Enantioselective Transformations Involving C–H Bond Cleavage by Transition-Metal Complexes

et al. 2017

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The development of new methods for the direct functionalization of unactivated C-H bonds is ushering in a paradigm shift in the field of retrosynthetic analysis. In particular, the catalytic enantioselective functionalization of C-H bonds represents a highly atom- and step-economic approach toward the generation of structural complexity. However, as a result of their ubiquity and low reactivity, controlling both the chemo- and stereoselectivity of such processes constitutes a significant challenge. Herein we comprehensively review all asymmetric transition-metal-catalyzed methodologies that are believed to proceed via an inner-sphere-type mechanism, with an emphasis on the nature of stereochemistry generation. Our analysis serves to document the considerable and rapid progress within in the field, while also highlighting limitations of current methods.

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Section: Kinetic Resolutionsmentioning

confidence: 99%

Catalytic Enantioselective Transformations Involving C–H Bond Cleavage by Transition-Metal Complexes

et al. 2017

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“…The unique biological profile of brefeldin A, C, and analogues has attracted a lot of interest in the synthetic organic chemistry community. The first synthesis of the racemic brefeldin A was reported by Corey and Wollenberg in 1976 followed by around 40 total and formal syntheses . Brefeldin C was prepared for the first time by total synthesis in 1988 by Schreiber and Meyers followed by Takano, Guingant (along with aspects of the biological properties of BFA) and Tsunoda .…”

Section: Figurementioning

confidence: 99%

A Short Synthesis of (+)‐Brefeldin C through Enantioselective Radical Hydroalkynylation

Gnägi

Martz

Meyer

et al. 2019

Chemistry A European J

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Av ery conciset otal synthesis of (+ +)-brefeldin C starting from 2-furanylcyclopentene is described. This approach is based on an unprecedented enantioselective radical hydroalkynylation process to introduce the two cyclopentanes tereocenters in as ingle step. The use of a furan substituent allows ah igh trans diastereoselectivity to be achieved duringt he radicalp rocess and it contains the four carbona toms C1-C4 of the natural product in an oxidation state closely relatedt ot he one of the target molecule. The eight-step synthesis requires six product purifications and it provides (+ +)-brefeldin Ci n1 8% overall yield.[**] Ap revious versiono ft his manuscript has been deposited on ap reprint server (https://doi.org/10.26434/chemrxiv.8397731.v1)Supporting information and the ORCID identification number(s) for the author(s) of this articlecan be found under: https://doi.

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“…2) After that, this hydroacylation of 4-alkenals has been expanded to a catalytic process 3,4) and asymmetric reaction. [5][6][7][8][9][10][11][12][13][14][15][16][17][18] The proposed reaction mechanism is shown in Chart 1. Initially, oxidative addition of the C-H bond of the aldehyde moiety to the rhodium complex occurs to form acylrhodium intermediate i followed by insertion of an alkene moiety to the Rh-H bond to give the 6-membered rhodacycle intermediate ii.…”

Section: Introductionmentioning

confidence: 99%

“…16,17) However, it is difficult to expand this hydroacylation to the construction of larger sized carbocyclic ring compounds because the side reactions are in competition with other reactions such as decarbonylation of the carbonyl group and isomerization of the alkene moiety in the substrate. In 1991, Gable and Benz reported that hydroacylation of 5-alkenals 3 afforded the 6-membered ring ketone 4 in moderate yield even though they used a 30 mol% Rh(I) complex 19) (Chart 2, eq.…”

Section: Introductionmentioning

confidence: 99%

Development of Novel Cyclizations <i>via</i> Rhodacycle Intermediate and Its Application to Synthetic Organic Chemistry

Oonishi

2015

Chem. Pharm. Bull.

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Novel Rh(I)-catalyzed cyclizations through a different type of rhodacycle intermediate which is formedby hydroacylation of 4,6-dienal or oxidative addition of diene and alkene are described. Hydroacylation of 4,6-dienal afforded various 7-membered rings in good to high yields, while cycloisomerization of diene and alkene provided 5-or 6-membered rings in good yields. On the basis of these studies, we have also succeeded in developing the sequential reaction of hydroacylation followed by cycloisomerization to produce bicyclic compounds in a stereoselective manner and thus this reaction was expanded to the synthesis of epiglobulol. Furthermore, both Rh(I)-catalyzed hydroacylation and cycloisomerization using ionic liquid (IL) as a solvent were investigated and it was found that the IL recovered after the reaction, which contains the Rh(I) catalyst, could be recycled several times without loss of catalytic activity.

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Enantioconvergent Formal Synthesis of Brefeldin A via Sakai-Catalyzed Cyclization

Cited by 25 publications

References 29 publications

Catalytic Enantioselective Transformations Involving C–H Bond Cleavage by Transition-Metal Complexes

Catalytic Enantioselective Transformations Involving C–H Bond Cleavage by Transition-Metal Complexes

A Short Synthesis of (+)‐Brefeldin C through Enantioselective Radical Hydroalkynylation

Development of Novel Cyclizations <i>via</i> Rhodacycle Intermediate and Its Application to Synthetic Organic Chemistry

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