A regio- and stereoselective synthesis of trisubstituted alkenes via gold(i)-catalyzed hydrophosphoryloxylation of haloalkynes

Chary, Bathoju Chandra; Kim, Sunggak; Shin, Doosup; Lee, Phil Ho

doi:10.1039/c1cc12052b

Cited by 35 publications

(15 citation statements)

References 57 publications

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“…Only one work dealing with this type of transformations can be currently found in the literature, in which the addition of diphenyl phosphate to different bromo-and iodoalkynes was successfully achieved by using catalytic amounts of the cationic species [Au(PPh 3 )] + , generated in situ from the chloride complex [AuCl(PPh 3 )] and silver triflate (Scheme 31). [58] The resulting alkenyl-halophosphate products 52 were generated with complete regio-and Z-stereoselectivity as the result of the expected anti addition of O-H bond of (PhO) 2 P(=O)OH to the gold-π complexed alkyne. The utility of 52 as coupling partners in palladium catalyzed Sonogashira, Kumada-Corriu, Suzuki and Stille reactions was also demonstrated by the authors.…”

Section: Hydrophosphoryloxylation Reactionsmentioning

confidence: 99%

Metal‐Catalyzed Hydrofunctionalization Reactions of Haloalkynes

Cadierno

2019

Eur J Inorg Chem

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Metal‐catalyzed hydrofunctionalization reactions of alkynes, i.e. the addition of E–H units (E = heteroatom or carbon) across the C≡C bond, are of key importance in modern synthetic chemistry. In recent years, haloalkynes have been successfully involved in these types of transformations, thus opening new atom‐economical routes for the generation, among others, of haloalkenes, a pivotal class of compounds for cross‐coupling processes. In particular, several catalytic systems able to promote the selective addition of C–H, O–H, N–H, S–H and X–H (X = halide) bonds to haloalkynes have been reported. This chemistry is comprehensively discussed in this Minireview article.

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Section: Hydrophosphoryloxylation Reactionsmentioning

confidence: 99%

Metal‐Catalyzed Hydrofunctionalization Reactions of Haloalkynes

Cadierno

2019

Eur J Inorg Chem

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“…Nevertheless, the synthesis of triflates is expensive and corrosive, making alternatives attractive. As a coupling partner, alkenyl phosphates have been proven reactive in most metal-catalyzed cross-coupling reactions, such as Stille, [4,8] SuzukiMiyaura, [5] Negishi, [6] Kumada, [7] Sonogashira, [8] and Mizoroki-Heck. [9] Alkenyl phosphate synthesis most often involves the conversion of carbonyl compounds into enolates by base-promoted proton extraction followed by reaction with dialkyl phosphorochloridates.…”

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confidence: 99%

Gold(I)‐Catalyzed Stereoselective Synthesis of Alkenyl Phosphates by Hydrophosphoryloxylation

Nun

Egbert

Oliva-Madrid

et al. 2011

Chemistry A European J

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“…Using this method, the authors could regioand stereoselectively produce a variety of phosphorylated (Z)β-haloenol ethers 977 (Scheme 228, part A). 399 In the same study, these haloalkenes were shown to be efficient partners in palladium-mediated cross-coupling reactions to afford stereodefined trisubstituted alkenes. The same group later described the intramolecular addition of hydrogen phosphates to alkynes and were able to selectively obtain cyclic Z-iodo vinyl phosphates in high yields (Scheme 228, part B).…”

Section: Haloalkynesmentioning

confidence: 95%

Gold-Catalyzed Reactions of Specially Activated Alkynes, Allenes, and Alkenes

et al. 2020

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This review describes the gold-catalyzed reactions of specially activated alkynes, allenes, and alkenes. Such species are characterized by the presence of either electron-donating or electron-withdrawing groups as substituents of the carbon π-system. They are intrinsically polarized, and when compared to their nonspecially activated counterparts can therefore be involved in gold-catalyzed transformations featuring increased regio-, stereo-, and chemoselectivities. The chemistry of specially activated carbon π-systems under homogeneous gold catalysis is extremely rich and varied. The reactivity observed with nonspecially activated unsaturated systems can often be transposed to specially activated ones without loss of efficiency. However, specially activated carbon π-systems also exhibit specific reactivities that cannot be attained with regular substrates. In this family of carbon π-systems, ynamides and their analogs, along with alkynyl carbonyl derivatives, are the classes of substrates that have retained the most attention. This review provides an overview of the chemistry developed with all classes of specially activated carbon π-systems by discussing their general and specific reactivities, presenting and commenting on their gold-catalyzed transformations as well as their applications.

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A regio- and stereoselective synthesis of trisubstituted alkenes via gold(i)-catalyzed hydrophosphoryloxylation of haloalkynes

Abstract: A new stereoselective synthesis of trisubstituted alkenes is developed. Hydrophosphoryloxylation of haloalkynes provides Z-alkenyl halophosphates, which undergo Pd-catalyzed consecutive cross-coupling reactions to afford regio- and stereodefined trisubstituted alkenes.

Cited by 35 publications

References 57 publications

Metal‐Catalyzed Hydrofunctionalization Reactions of Haloalkynes

Metal‐Catalyzed Hydrofunctionalization Reactions of Haloalkynes

Gold(I)‐Catalyzed Stereoselective Synthesis of Alkenyl Phosphates by Hydrophosphoryloxylation

Gold-Catalyzed Reactions of Specially Activated Alkynes, Allenes, and Alkenes

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