Synthesis of terbinafine. A palladium catalyzed vinyl iodide-ethynylstannane coupling

Rudisill, Duane E.; Castonguay, Laurie A.; Stille, J. K.

doi:10.1016/s0040-4039(00)80338-x

Cited by 23 publications

(11 citation statements)

References 9 publications

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“…The structure of intermediate 4a was investigated during in situ NMR reaction monitoring, since it was too unstable for other methods. Finally, the formation of 4a is suggested to be concluded via an [1,3]-H shift generating alt-4 and the subsequent addition of water (for other potential mechanisms to intermediate 4 and their exclusion see SI). To identify heteroatoms and their connectivity in 4a theoretical calculations and 15 N-isotope labelling were applied.…”

Section: Resultsmentioning

confidence: 99%

“…Dynemicin A, [1] Terbinafine [2,3] (Lamisil®), callipeltosides [4] or Neocarzinostatin [5] ], nitronates, especially cyclic nitronates, find application in the synthesis of biologically active compounds, [6,7] drug candidates [8][9][10] and natural products. While the structural motif of a conjugated enyne occurs in many pharmaceuticals and natural compounds [e.g.…”

Section: Introductionmentioning

confidence: 99%

“…While the structural motif of a conjugated enyne occurs in many pharmaceuticals and natural compounds [e.g. [3,[12][13][14][15][16][17] Although metal-free procedures, especially organocatalytic ones, to conjugated enynes would be very valuable, they are rarely found in literature. [11] Due to the fundamental structural dissimilarities between cyclic nitronates and conjugated enynes, these compounds are generally accessed by disparate strategies.…”

Section: Introductionmentioning

confidence: 99%

“…While the structural motif of a conjugated enyne occurs in many pharmaceuticals and natural compounds [e.g. Dynemicin A, [1] Terbinafine [2,3] (Lamisil®), callipeltosides [4] or Neocarzinostatin [5] ], nitronates, especially cyclic nitronates, find application in the synthesis of biologically active compounds, [6,7] drug candidates [8][9][10] and natural products. [11] Due to the fundamental structural dissimilarities between cyclic nitronates and conjugated enynes, these compounds are generally accessed by disparate strategies.…”

Section: Introductionmentioning

confidence: 99%

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Unprecedented Mechanism of an Organocatalytic Route to Conjugated Enynes with a Junction to Cyclic Nitronates

et al. 2018

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Conjugated enynes as well as cyclic nitronates are crucial building blocks for numerous natural products and pharmaceuticals. However, so far, no common and metal‐free synthetic route to both conjugated enynes and cyclic nitronates has been reported. Herein, in situ NMR, labelling studies and theoretical calculations were combined to investigate the mechanism of the unusual triple bond formation towards conjugated enynes. Starting from nitroalkene dimers, first an isoxazolidine‐2,5‐diol derivative is formed as central intermediate. From this, enynes were generated by a combination of oxidation, dehydration, and retro 1,3‐dipolar cycloaddition, whereas for nitronates a base induced intramolecular reorganization is proposed. While the product distribution could be controlled and high yields of nitronate were achieved, only medium to good yields for enynes were obtained due to polymerization losses. Nevertheless, we hope that these mechanistic investigations may provide a basis for further developments of organocatalytic or metal‐free preparations of conjugated enynes and nitronates.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Unprecedented Mechanism of an Organocatalytic Route to Conjugated Enynes with a Junction to Cyclic Nitronates

et al. 2018

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“…(24)] [36]. Using this procedure, the thienylacetylene 66, which is an intermediate for the synthesis of a natural antifungal and nematicidal agent can be prepared [Eq.…”

Section: Alkynylmagnesium Reagentsmentioning

confidence: 99%

Cross‐Coupling Reactions to sp Carbon Atoms

Sonogashira¹

1998

Metal‐Catalyzed Cross‐Coupling Reactions

216

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TheStille Reaction

1997

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Examples of the palladium‐catalyzed coupling of organotin compounds with carbon electrophiles were first reported in 1977 by Kosugi, Shimizu, and Migita. The first study by Stille appeared in 1978. The early work of Beletskaya, using “ligandless” catalysts in cross‐coupling reactions, also often employed organostannanes. In recognition of Stille's comprehensive synthetic and mechanistic studies, this coupling is now referred to as the Stille reaction. R 1 is typically an unsaturated moiety (e.g., vinyl, aryl, heteroaryl, alkynyl, allyl) or less often an alkyl group, and R 2 , the nontransferable ligand, is almost always butyl or methyl. Electrophiles participating in the coupling include halides (almost always bromides or iodides) and sulfonates (most often used are the triflates). Other leaving groups have been used in special cases. The Stille reaction belongs to the larger family of palladium‐ and nickel‐catalyzed cross‐coupling reactions which features, e.g., organomagnesium, organozinc, organoboron, and organosilicon reagents. Organotin reagents are air‐ and moisture‐stable organometallics, and can be conveniently purified and stored. Since they do not react with most common functional groups, the use of protecting groups is almost always unnecessary in conjunction with the Stille reaction. This is a very unusual and attractive feature for an organometallic process. Also, the reaction is often neither air nor moisture sensitive. In some cases, water and oxygen have actually been shown to promote the coupling. Although the reaction as initially described by Stille is often carried out under rather drastic conditions (temperatures of ≥100° are not uncommon), newly developed ligand 11 and the addition of copper(I) salts have solved some of the problems associated with low reactivity. The utility and mildness of the Stille reaction are demonstrated by its frequent use in the final stages of complex natural product syntheses. This chapter attempts a critical and comprehensive coverage of the reaction scope. Mechanistic description of the reaction is rather brief, and the reader is referred to the pertinent literature for a more detailed analysis. All of the relevant literature is covered up to the end of 1994. The reaction was reviewed by Stille in 1986, and by Mitchell in 1992; a rather comprehensive account by Farina and Roth has appeared more recently. Developments that occurred in 1995, as this work was in progress, and that were deemed important were incorporated as much as possible in this review.

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Synthesis of terbinafine. A palladium catalyzed vinyl iodide-ethynylstannane coupling

Cited by 23 publications

References 9 publications

Unprecedented Mechanism of an Organocatalytic Route to Conjugated Enynes with a Junction to Cyclic Nitronates

Unprecedented Mechanism of an Organocatalytic Route to Conjugated Enynes with a Junction to Cyclic Nitronates

Cross‐Coupling Reactions to sp Carbon Atoms

TheStille Reaction

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