Tertiary arsine ligands for the Stille coupling reaction

Chishiro, Akane; Konishi, M.; Inaba, Ryoto; Yumura, Takashi; Imoto, Hiroaki; Naka, Kensuke

doi:10.1039/d1dt02955j

Cited by 11 publications

(6 citation statements)

References 43 publications

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“…The iodoacrylate is more reactive towards Pd insertion than the bromoacrylate, thus favoring this productive reaction (step 1) compared to the insertion of Pd into the C-S bond. This selectivity is expected to be even more pronounced at room temperature than at 50 • C. The addition of AsPh 3 supports these effects by accelerating both the formation of the active Pd(0) from the Pd(II) species and transmetallation, due to its lower σ-donor effect than PPh 3 [31,32].…”

Section: Resultsmentioning

confidence: 88%

Suzuki–Miyaura Reaction in the Presence of N-Acetylcysteamine Thioesters Enables Rapid Synthesis of Biomimetic Polyketide Thioester Surrogates for Biosynthetic Studies

2023

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Biomimetic N-acetylcysteamine thioesters are essential for the study of polyketide synthases, non-ribosomal peptide synthetases and fatty acid synthases. The chemistry for their preparation is, however, limited by their specific functionalization and their susceptibility to undesired side reactions. Here we report a method for the rapid preparation of N-acetylcysteamine (SNAC) 7-hydroxy-2-enethioates, which are suitable for the study of various enzymatic domains of megasynthase enzymes. The method is based on a one-pot sequence of hydroboration and the Suzuki–Miyaura reaction. The optimization of the reaction conditions made it possible to suppress potential side reactions and to introduce the highly functionalized SNAC methacrylate unit in a high yield. The versatility of the sequence was demonstrated by the synthesis of the complex polyketide-SNAC thioesters 12 and 33. Brown crotylation followed by the hydroboration to Suzuki–Miyaura reaction sequence enabled the introduction of the target motif in significantly fewer steps and with a higher overall yield and stereoselectivity than previously described approaches. This is the first report of a transition-metal-catalyzed cross-coupling reaction in the presence of an SNAC thioester.

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Section: Resultsmentioning

confidence: 88%

Suzuki–Miyaura Reaction in the Presence of N-Acetylcysteamine Thioesters Enables Rapid Synthesis of Biomimetic Polyketide Thioester Surrogates for Biosynthetic Studies

2023

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“…AsR 3 ( L1 – L13 ) and Buchwald-type ( L14 – L20 ) arsine ligands were prepared according to a procedure previously reported by our group (Scheme ). , Density functional theory (DFT) calculations were conducted to estimate the structural and electronic properties of the ligands such as Tolman’s electronic parameter (TEP), Crabtree’s DFT computational electronic parameter (CEP), cone angle (θ), and percent buried volume (% V bur ) (Table S3). , The activities of the Pd catalysts with ligands L1 – L20 were examined.…”

Section: Results and Discussionmentioning

confidence: 99%

“…Our group has developed practical synthetic methods for organoarsenic compounds using nonvolatile precursors. Tribromoarsine (AsBr 3 ) is a key precursor because it is less volatile than trichloroarsine (AsCl 3 ); the vapor pressures are 1 mmHg (41.8 °C, AsBr 3 ) and 10 mmHg (23.5 °C, AsCl 3 ) . AsBr 3 is prepared from arsenic trioxide (As 2 O 3 ) and hydrobromic acid (HBr) in almost quantitative yield .…”

Section: Introductionmentioning

confidence: 99%

Tertiary Arsine Ligands for Pd-Catalyzed Direct Arylation

Ogawa,

Sumida,

Yumura

et al. 2024

Organometallics

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Catalysts for direct arylations have been extensively studied for the efficient synthesis of (hetero)biaryl compounds. Phosphine ligands are pivotal in this field, and electron-deficient phosphine ligands are advantageous for direct arylation. Due to its relatively weak σ-donation ability, arsenic is considered an ideal candidate for designing electron-deficient ligands. However, no studies have explored the relationship between the structure of the arsine ligands and their catalytic activity for direct arylation. In this study, we synthesized 27 arsine ligands with varying electrondonating and steric properties. Tris(o-trifluorotolyl)arsine, an electron-deficient and bulky ligand, exhibited the highest efficiency in a model reaction between 2-propylthiophene and 4-bromobenzotrifluoride. Both experimental and computational studies revealed the mechanism of direct arylation using arsine ligands. This is the first comprehensive investigation of an arsine-ligated catalytic direct arylation.

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“…1,2-Dibromobenzene, bromopentafluorobenzene, 1-bromo-3,5-bis(trifluoromethyl)benzene, 4-bromoanisole, anisole, triphenylantimony (SbPh 3 ), dimethyl terephthalate and o -chloranil were purchased from Tokyo Chemical Industry Co., Ltd (Tokyo, Japan). 2,2′-Dibromobiphenyl, 20 tetrachlorocatecholato-triphenylarsine ( 1 ), 14 a 9-phenyl-9-arsafluorene ( 4′ ), 12 a 9-iodo-9-arsafluorene, 12 b 9-pentafluorophenyl-9-arsafluorene ( 6′ ), 21 tris(3,5-bis(trifluoromethyl)phenyl)arsine, 22 tris( p -anisyl)arsine, 7 dithieno[3,2- b :2′,3′- d ]arsole ( 8′ ), 13 9-phenyl-9-phosphafluorene ( 11′ ), 10 tetrachlorocatecholato-triphenylphosphine ( 9 ), 14 a tetrachlorocatecholato-triphenylstibine ( 10 ), 14 a and tetrachlorocatecholato-9-phenyl-9-stibafluorene ( 12 ) 14 b were prepared according to the literature procedures.…”

Section: Methodsmentioning

confidence: 99%