CO Surrogate for Ester, Thioester and Amide Synthesis via Carbonylation

2,4,6-Trichlorophenyl Formate [T3121] is a stable crystalline solid at room temperature that serves as a solid carbon monoxide surrogate for carbonylation. Upon treatment with a trialkylamine it decomposes rapidly, and the CO generated in situ is applied to the carbonylation of aryl or alkenyl halides (X = I, Br, OTf) with Pd(OAc)2/Xantphos and NR3¹)²). Reaction with the nucleophiles OR2, SR2 and NR2 gives esters, thioesters and amides. TCI's Practical Example shows 2-iodofluorene carbonylated at room temperature, followed by reaction with morpholine and DMAP at 45 °C to obtain the amide. N-Formylsaccharin [F0854] is used with Pd(OAc)2, Ph2P(CH2)4PPh2, triethylsilane and Na2CO3 for the reductive carbonylation of aryl bromides, 3-bromopyridine and 2-bromothiophene to the corresponding aldehydes in DMF at 75–85 °C³).

Related products

• TCI T3121 4525-65-9 2,4,6-Trichlorophenyl Formate
• TCI F0854 50978-45-5 N-Formylsaccharin
• TCI A1424 3375-31-3 Palladium(II) Acetate
• TCI B2709 161265-03-8 4,5-Bis(diphenylphosphino)-9,9-dimethylxanthene
• TCI P2161 3375-31-3 Palladium(II) Acetate (Purified)

References

1. Trichlorophenyl Formate: Highly Reactive and Easily Accessible Crystalline CO Surrogate for Palladium-Catalyzed Carbonylation of Aryl/Alkenyl Halides and Triflates. T. Ueda, H. Konishi, K. Manabe, Org. Lett. 2012, 14, 5370. doi:10.1021/ol302593z
2. Pd-Catalyzed External-CO-Free Carbonylation: Preparation of 2,4,6-Trichlorophenyl 3,4-Dihydronaphthalene-2-Carboxylate. H. Konishi, T. Ueda, K. Manabe, Org. Synth. 2014, 91, 39. doi:10.15227/orgsyn.091.0039
3. Palladium‐Catalyzed Reductive Carbonylation of Aryl Halides with N ‐Formylsaccharin as a CO Source. T. Ueda, H. Konishi, K. Manabe, Angew. Chem. Int. Ed. 2013, 52, 8611. doi:10.1002/anie.201303926

Download TCI brochure Carbon Monoxide (CO) Surrogate Reagents for Carbonylation (PDF)

Source

• TCI Practical Example: www.tcichemicals.com/ID/en/product/tci-topics/TCIPracticalExample_20240304
• TCI product page T3121: tcichemicals.com/ID/en/p/T3121
• TCI product page F0854: tcichemicals.com/ID/en/p/F0854
• TCI brochure RR070: Carbon Monoxide (CO) Surrogate Reagents for Carbonylation

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