Palladacycles derived from arylphosphinamides for mild Suzuki–Miyaura cross-couplings

Wu, Guo‐Jie; Han, Fuzhu; Zhao, Yu‐Long

doi:10.1039/c5ra12742d

Cited by 19 publications

(12 citation statements)

References 52 publications

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“…Accordingly, we shifted our focus to a phosphinamide-based palladacycle catalyst 16, which was developed previously by our group (Du et al., 2015, Guan et al., 2014). A supportive clue, albeit not tightly related with the proposed Heck-type reaction, that encouraged us to inspect this catalyst herein is that 16 exhibited extremely high catalytic activity for mild Suzuki coupling of a broad range of arene ( pseudo )halides (Wu et al., 2015, Wu et al., 2018, Cao et al., 2018). To our delight, the use of 16 as catalyst did improve substantially the yield of 15a to 72% (entry 4).…”

Section: Resultsmentioning

confidence: 99%

Pd-Catalyzed Aerobic Oxidative Heck Cross-Coupling for the Straightforward Construction of Indole δ-Lactams

Zhang

Han

2019

iScience

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Summary The [6.5.6]-tricyclic indole δ-lactam represents a common key intermediate for the synthesis of a broad variety of structurally intriguing indole alkaloids. The development of a method for the versatile and straightforward construction of such structural motif is of great importance for potential synthetic applications. Herein, we present a co-ligand-prompted Pd-catalyzed 6- exo - trig intramolecular cyclization of indolyl amides via the aerobic oxidative Heck cross-coupling. The method provided a general and efficient way for the construction of [6.5.6]-tricyclic indole δ-lactams. A mechanistic study suggests that a Pd (I) /Pd (III) catalytic cycle should be responsible for effective coupling, which represents a mechanistically alternative pathway when compared with the Pd (0) /Pd (II) cycle proposed for other related coupling reactions.

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Section: Resultsmentioning

confidence: 99%

Pd-Catalyzed Aerobic Oxidative Heck Cross-Coupling for the Straightforward Construction of Indole δ-Lactams

Zhang

Han

2019

iScience

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“…To compare with the prior literature 27 – 31 , the low coupling efficiency is probably due to the excessively congested structure of 15a with the additional presence of a bulky OTBS. To overcome this obstacle, we turned to examine the catalytic efficiency of phosphinamide-derived palladacycle 18 , which was developed in our previous studies toward synthesizing P-stereogenic compounds through C–H arylation of phosphinamide 32 , 33 and exhibited excellent catalytic activity for Suzuki cross-coupling of aryl (pseudo)halides under mild conditions 34 . To our delight, we found that the palladacycle 18 did display high catalytic activity for such a heavily substituted nonactivated triflate 15a .…”

Section: Resultsmentioning

confidence: 99%

Total synthesis of cyrneines A–B and glaucopine C

Zhang

Tan

et al. 2018

Nat Commun

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The cyrneine diterpenoids represent a structurally intriguing subfamily of cyathane diterpenoids and could significantly induce neurite outgrowth. Therefore, the efficient synthesis of these natural products is of great importance. Herein, we present a route for the collective synthesis of cyrneines A, B, and glaucopine C. As the key precursor, the 5-6-6-tricyclic scaffold is efficiently constructed by employing a mild Suzuki coupling of heavily substituted nonactivated cyclopentenyl triflate and a chelation-controlled regiospecific Friedel-Crafts cyclization as key transformations. The stereoselective installation of the all-carbon quaternary center at C6 ring junction of the tricycle is achieved via Birch reductive methylation. Subsequently, a carbenoid-mediated ring expansion furnishes the essential 5-6-7-tricyclic core. Finally, manipulation of this core by several appropriately orchestrated conversions accomplishes a more step-economic synthesis of cyrneine A (20 steps), and the first synthesis of cyrneine B (24 steps) and glaucopine C (23 steps).

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“…1 2-(3,5-Difluorophenyl)naphthalene (3u). 25 White solid (36 mg, 75%); mp 118.5−119.6 °C. Petroleum ether.…”

Section: -(Naphthalen-2-yl)benzo[d]mentioning

confidence: 99%

Synthesis of Biaryls via Decarbonylative Nickel-Catalyzed Suzuki–Miyaura Cross-Coupling of Aryl Anhydrides

et al. 2020

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Transition metal-catalyzed cross-couplings have been widely employed in the synthesis of many important molecules in synthetic chemistry for the construction of diverse C−C bonds. Conventional cross-coupling reactions require active electrophilic coupling partners, such as organohalides or sulfonates, which are not environmentally friendly enough. Herein, we disclose the first nickel-catalyzed Suzuki−Miyaura cross-coupling of aryl anhydrides and arylboronic acids for the synthesis of biaryls in a decarbonylation manner. The reaction tolerates a wide range of electron-withdrawing, electron-neutral, and electron-donating substituents in this process.

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Palladacycles derived from arylphosphinamides for mild Suzuki–Miyaura cross-couplings

Cited by 19 publications

References 52 publications

Pd-Catalyzed Aerobic Oxidative Heck Cross-Coupling for the Straightforward Construction of Indole δ-Lactams

Pd-Catalyzed Aerobic Oxidative Heck Cross-Coupling for the Straightforward Construction of Indole δ-Lactams

Total synthesis of cyrneines A–B and glaucopine C

Synthesis of Biaryls via Decarbonylative Nickel-Catalyzed Suzuki–Miyaura Cross-Coupling of Aryl Anhydrides

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