1394389-42-4Relevant articles and documents
Mechanism and Scope of Nickel-Catalyzed Decarbonylative Borylation of Carboxylic Acid Fluorides
Malapit, Christian A.,Bour, James R.,Laursen, Simon R.,Sanford, Melanie S.
, p. 17322 - 17330 (2019)
This Article describes the development of a base-free, nickel-catalyzed decarbonylative coupling of carboxylic acid fluorides with diboron reagents to selectively afford aryl boronate ester products. Detailed studies were conducted to assess the relative rates of direct transmetalation between aryl boronate esters and diboron reagents and a bisphosphine nickel(aryl)(fluoride) intermediate. These investigations revealed that diboron reagents undergo transmetalation with this Ni(aryl)(fluoride) intermediate at rates significantly faster than their aryl boronate ester congeners. Furthermore, the reactivity of both boron reagents toward transmetalation is enhanced with increasing electrophilicity of the boron center. These mechanistic insights were leveraged to develop a catalytic decarbonylative borylation of acid fluorides that proved applicable to a variety of (hetero)aryl carboxylic acid fluorides as well as diverse diboron reagents. The acid fluorides can be generated in situ directly from carboxylic acids. Furthermore, the mechanistic studies directed the identification of various air-stable Ni pre-catalysts for this transformation.
Synthesis of [11C]Am80 via novel Pd(0)-mediated rapid [ 11C]carbonylation using arylboronate and [11C]Carbon Monoxide
Takashima-Hirano, Misato,Ishii, Hideki,Suzuki, Masaaki
supporting information, p. 804 - 807 (2013/01/15)
11C-labeled methylbenzoates [11C]4a-d were synthesized using Pd(0)-mediated rapid cross-coupling reactions employing [ 11C]carbon monoxide and arylboronic acid neopentyl glycol esters 3a-d under atmospheric pressure in methanol-dimethylformamide (MeOH-DMF), in radiochemical yields of 12 ± 5-26 ± 13% (decay-corrected based on [11C]O). The reaction conditions were highly favorable for the synthesis of [11C]Am80 ([11C]2) and [11C]methyl 4-((5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-yl)carbamoyl)benzoate ([11C]2-Me) using 4-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-N-(5,5,8, 8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-yl)benzamide (5), both of which produced a decay-corrected radiochemical yield (RCY) of 26 ± 13%, with >99% radiochemical purity and an average specific radioactivity of 44 GBq/μmol. The yields of [11C]4a, [11C]2-Me, and [ 11C]2 were improved by the use of a 2-fold excess of the solvents and reagents under the same conditions to give respective yields of 66 ± 8, 65 ± 7, and 48 ± 2%.
