Synthesis of Dimeric Steroid Trioxabispiroacetals Scaffolds by Gold(I)‐Catalyzed Hydroalkoxylation–Hydration of Diynediols

Valdez-García, Ricardo M.; Alarcón-Manjarrez, Carlos; Galano, Annia; Rodrı́guez-Molina, Braulio; Flores‐Álamo, Marcos; Iglesias-Arteaga, Martı́n A.

doi:10.1002/ejoc.201900860

Cited by 14 publications

(7 citation statements)

References 65 publications

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“…In complete agreement with the trans/cis ratio experimentally observed (69:31), the computations indicated a slightly lower energy for the trans isomer (1.08 Kcal/mol). Employing the cationic gold(I) complex [Au(NCMe)(JohnPhos)][SbF 6 ] as a catalyst, the related bis-spiroketals 113-115 were synthesized by Iglesias-Arteaga and colleagues through the hydroalkoxylation/hydration of the respective steroid-derived diynediols (Figure 15) [165]. The double spiroacetalization process proceeded in high yields (≥68%) and produced almost exclusively the C 2 symmetrical trans distereoisomers (only in the case of 115 was a small amount of the unsymmetrical cis isomer formed).…”

Section: Hydroalkoxylation Processesmentioning

confidence: 99%

Catalytic Hydrofunctionalization Reactions of 1,3-Diynes

Cadierno

2022

Catalysts

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Metal-catalyzed hydrofunctionalization reactions of alkynes, i.e., the addition of Y–H units (Y = heteroatom or carbon) across the carbon–carbon triple bond, have attracted enormous attention for decades since they allow the straightforward and atom-economic access to a wide variety of functionalized olefins and, in its intramolecular version, to relevant heterocyclic and carbocyclic compounds. Despite conjugated 1,3-diynes being considered key building blocks in synthetic organic chemistry, this particular class of alkynes has been much less employed in hydrofunctionalization reactions when compared to terminal or internal monoynes. The presence of two C≡C bonds in conjugated 1,3-diynes adds to the classical regio- and stereocontrol issues associated with the alkyne hydrofunctionalization processes’ other problems, such as the possibility to undergo 1,2-, 3,4-, or 1,4-monoadditions as well as double addition reactions, thus increasing the number of potential products that can be formed. In this review article, metal-catalyzed hydrofunctionalization reactions of these challenging substrates are comprehensively discussed.

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Section: Hydroalkoxylation Processesmentioning

confidence: 99%

Catalytic Hydrofunctionalization Reactions of 1,3-Diynes

Cadierno

2022

Catalysts

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“…So far, only a few gold-catalyzed functionalizations of 1,3-butadiynes can be found in literature and functionalizations using O-nucleophiles are, in contrast to alkyne substrates, rarely know. [22,[39][40][41][42] One of these examples is a cyclization of 1,3-butadiyne developed by Skrydstrup et al in 2010. [20] The two-fold 1,4addition of a bis-nucleophile enables the synthesis of pyrrole or furan derivatives, which are of particular interest due to their biologically activity.…”

Section: Introductionmentioning

confidence: 99%

Gold Catalysis: 2,3‐ or 1,4‐Addition to Butadiynes

Stein¹,

Pascher²,

Stracke³

et al. 2022

Adv Synth Catal

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In the past, numerous impressive methodologies have been developed in homogeneous gold catalysis, typically using alkynes, allenes, or different non‐conjugated diyne systems as starting materials. While there are applications catalyzed by other transition metals, the use of 1,3‐butadiyne derivatives has been largely neglected in gold catalysis. In this work we present an efficient gold‐catalyzed method focusing on the functionalization of this specific type of diynes. The starting materials can be synthesized via simple Glaser Coupling, starting from cheap, highly variable, terminal alkynes. These homocoupling products, which are often observed as undesirable side‐products in Sonogashira reactions, can be converted into versatile 1,3‐butadiene derivatives in alcohol as a solvent and nucleophile under mild conditions. The possible field of application of the 1,3‐butadiene derivatives known from the literature is very broad and ranges from a use as transistor or OLED material to a use as an enzyme inhibitor. The approach presented here offers an attractive and highly effective way to versatile functionalized 1,3‐butadiene derivatives.

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“…As a part of our ongoing project on the development and study of the properties of crystalline materials based on steroid dimers, we have previously described the synthesis of several compounds that show properties as molecular rotors or interesting supramolecular arrays. , In particular, we have described the synthesis of a dimeric steroid scaffold employing the Au(I)-catalyzed hydroalkoxylation–hydration of steroid diynediols. The V-shaped structure of the symmetric dimer in which the two steroid cores are bridged by a 6,5,6-trioxabispiroacetal moiety produced a crystalline material with channels that propagate across the array (Figure ).…”

Section: Introductionmentioning

confidence: 99%

Palladium-Catalyzed Generation of ortho-Quinone Methides. A Three-Component Synthesis of L-Shaped Dimeric Steroidal Scaffolds

et al. 2021

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A series of hybrid dimers having orthogonal steroidal cores bridged by a chroman ketal moiety were obtained by Pd-catalyzed three-component reactions of steroid alkynols, 2-formylestradiol 17-monoacetate, and methyl orthoformate, via ortho-quinone methide intermediates. One of the obtained L-shaped scaffolds showed an inefficient crystal packing featuring large channels within the crystal array. Monte Carlo simulations indicate that these voids preferentially allocate n-hexane, opening the way to explore further applications of similar organic crystalline materials as selective hosts for small molecules.

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Synthesis of Dimeric Steroid Trioxabispiroacetals Scaffolds by Gold(I)‐Catalyzed Hydroalkoxylation–Hydration of Diynediols

Cited by 14 publications

References 65 publications

Catalytic Hydrofunctionalization Reactions of 1,3-Diynes

Catalytic Hydrofunctionalization Reactions of 1,3-Diynes

Gold Catalysis: 2,3‐ or 1,4‐Addition to Butadiynes

Palladium-Catalyzed Generation of ortho-Quinone Methides. A Three-Component Synthesis of L-Shaped Dimeric Steroidal Scaffolds

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