Oxidative Carbonylation as a Powerful Tool for the Direct Synthesis of Carbonylated Heterocycles

Abstract

Recent advances in the field of oxidative carbonylation reactions leading to carbonylated heterocyclic derivatives are presented (coverage: 2006 to the beginning of 2012).

Oscillatory carbonylation of phenylacetylene in the absence of externally supplied oxidant

“…6 [20], and explain recorded catalyst regeneration, Eq. 7 [21]. In order to validate the mechanism proposed in Scheme 1 and probe the behavior of the catalyst system in the absence of water, a series of pre-dried catalyst solutions of PdI 2 /KI of differing concentration were prepared.…”

(Z)-4-(Carbomethoxymethylene)-2-(4-fluorophenyl)-4H-benzo[d][1,3]oxazine

“…Palladium-catalyzed oxidative alkoxycarbonylation of alkynes is a simple and powerful tool for the synthesis of complex heterocyclic compounds from easily available starting reagents [1][2][3][4][5]. Over the years, we have successfully applied this effective methodology to access carbonylated compounds in a one-pot fashion [6][7][8][9][10][11][12][13].…”

“…Over the years, we have successfully applied this effective methodology to access carbonylated compounds in a one-pot fashion [6][7][8][9][10][11][12][13]. In particular, some years ago, we reported a facile and efficient route for the synthesis of new functionalized benzo [d] [1,3]oxazines by in situ deprotection of 2-(trimethylsilanyl)ethynylaniline derivatives followed by palladium-catalyzed cyclization-alkoxycarbonylation [14]. The benzo[d] [1,3]oxazine scaffold is found in many biologically active molecules, including anti-tumor, anti-inflammatory, anti-convulsant, and anti-fungal agents [15][16][17][18][19].…”

“…In particular, some years ago, we reported a facile and efficient route for the synthesis of new functionalized benzo [d] [1,3]oxazines by in situ deprotection of 2-(trimethylsilanyl)ethynylaniline derivatives followed by palladium-catalyzed cyclization-alkoxycarbonylation [14]. The benzo[d] [1,3]oxazine scaffold is found in many biologically active molecules, including anti-tumor, anti-inflammatory, anti-convulsant, and anti-fungal agents [15][16][17][18][19]. In this Note, we report the preparation of the fluorinated benzoxazine 2-that is, [1,3]oxazine-by adopting the same catalytic carbonylative strategy (Scheme 1).…”

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Abstract:The title compound, (Z)-4-(carbomethoxymethylene)-2-(4-fluorophenyl)-4H-benzo [d] [1,3] oxazine, was synthesized in 68% isolated yield by palladium-catalyzed oxidative cyclizationmethoxycarbonylation of 4-fluoro-N-(2-((trimethylsilyl)ethynyl)phenyl)benzamide. This new heterocyclic derivative was fully characterized by IR, 1 H-NMR, 13 C-NMR spectroscopies, MS spectrometry, and elemental analysis.

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