Gold(I)‐Catalyzed Enantioselective Synthesis of Pyrazolidines, Isoxazolidines, and Tetrahydrooxazines

LaLonde, Rebecca Lyn; Wang, Z. J.; Mba, Miriam; Lackner, Aaron D.; Toste, F. Dean

doi:10.1002/anie.200905000

Cited by 276 publications

(33 citation statements)

References 41 publications

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“…Disappointedly, only trace amounts of product was observed under the above conditions. Taking into account the counter ion effects in gold-catalyzed reactions [33–35], Ph 3 PAuOTf, produced from a combination of Ph 3 PAuCl and AgOTf in a 1:1 ratio, was investigated. To our delight, the expected product 2a could be isolated in 56% yield (Table 1, entry 2).…”

Section: Resultsmentioning

confidence: 99%

Au(I)/Au(III)-catalyzed Sonogashira-type reactions of functionalized terminal alkynes with arylboronic acids under mild conditions

Qian¹,

Zhang²

2011

Beilstein J. Org. Chem.

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Section: Resultsmentioning

confidence: 99%

Au(I)/Au(III)-catalyzed Sonogashira-type reactions of functionalized terminal alkynes with arylboronic acids under mild conditions

Qian¹,

Zhang²

2011

Beilstein J. Org. Chem.

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“…Part of the challenge of performing detailed kinetic studies of gold(I) catalyzed hydroamination reactions is that many of the most active catalysts employed are generated in situ from gold(I) trimers or the gold chloride and the corresponding silver salt, making it difficult to determine the precise concentration of catalyst employed 4. In 2009, we reported the intramolecular hydroamination reaction of allenes with hydrazine nucleophiles catalyzed by an isolable gold(I) complexes 5. We hypothesized that an intermolecular variant of this transformation could provide a valuable platform for a systematic study of the mechanism of the reaction.…”

Section: Introductionmentioning

confidence: 99%

Mechanistic Study of Gold(I)-Catalyzed Intermolecular Hydroamination of Allenes

et al. 2010

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The intermolecular hydroamination of allenes occurs readily with hydrazide nucleophiles, in the presence of 3-12% Ph 3 PAuNTf 2 . Mechanistic studies have been conducted to establish the resting state of the gold catalyst, the kinetic order of the reaction, the effect of ligand electronics on the overall rate, and the reversibility of the last steps in the catalytic cycle. We have found the overall reaction to be first order in gold and allene and zero order in nucleophile. Our studies suggest that the rate-limiting transition state for the reaction does not involve the nucleophile and that the active catalyst is monomeric in gold(I). Computational studies support an "outersphere" mechanism and predicts that a two-step, no intermediate mechanism may be operative. In accord with this mechanistic proposal, the reaction can be accelerated with the use of more electron deficient phosphine ligands on the gold(I) catalyst.

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“…Chiral piperidines could also be synthesized with good enantioselectivities; however, it was found that a related biphenyl bisphosphine complex (R)-ClMeO-BIPHEP (AuOPNB) 2 gave superior selectivities. The substrate scope was later expanded to include protected hydrazines and hydroxylamines to form chiral pyrazolidines and isoxazolidines [102].…”

Section: Asymmetric Hydroaminations Of Aminoallenesmentioning

confidence: 99%

Synthesis of Saturated Heterocycles via Metal-Catalyzed Alkene Hydroamination or Hydroalkoxylation Reactions

Julian

2013

Topics in Heterocyclic Chemistry

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The intramolecular hydrofunctionalization of carbon-carbon multiple bonds has emerged as a powerful way to form cyclic structures. A particularly important class of reactions involves the use of amine or alcohol nucleophiles, and alkenes or allenes as electrophiles, to form pyrrolidine, piperidine, tetrahydrofuran, and tetrahydropyran heterocycles in a highly efficient manner using late transition metal catalysts. Asymmetric methods for hydroamination and hydroalkoxylation reactions have recently emerged, allowing for the enantioselective synthesis of such saturated heterocycles. This review covers recent developments (over the last 5-10 years) in late transition metal-catalyzed hydroamination and hydroalkoxylation reactions that generate saturated heterocycles.

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Gold(I)‐Catalyzed Enantioselective Synthesis of Pyrazolidines, Isoxazolidines, and Tetrahydrooxazines

Cited by 276 publications

References 41 publications

Au(I)/Au(III)-catalyzed Sonogashira-type reactions of functionalized terminal alkynes with arylboronic acids under mild conditions

Au(I)/Au(III)-catalyzed Sonogashira-type reactions of functionalized terminal alkynes with arylboronic acids under mild conditions

Mechanistic Study of Gold(I)-Catalyzed Intermolecular Hydroamination of Allenes

Synthesis of Saturated Heterocycles via Metal-Catalyzed Alkene Hydroamination or Hydroalkoxylation Reactions

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