Peroxyester reaction of dimethylformamide

Rawlinson, D. J.; Humke, B. M.

doi:10.1016/s0040-4039(01)94324-2

Cited by 17 publications

(11 citation statements)

References 9 publications

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“…We anticipate that the amide product could be formed by the decarboxylation of carbamic anhydride intermediate B (Scheme ), which itself may be formed by the direct coupling of the acid with the formamide (Scheme , route 1) or through the formation of tert ‐butyl peroxybenzoate A (Scheme , route 2). Regarding route 2, Rawlinson and co‐workers showed that peroxyester A reacts with dimethylformamide in the presence of copper ions and subsequently transforms into the amide product 16. They proposed carbamic anhydride B as an intermediate, which decomposes into the amide with the loss of CO 2 .…”

Section: Resultsmentioning

confidence: 99%

Copper‐Catalyzed Oxidative Coupling of Carboxylic Acids with N,N‐Dialkylformamides: An Approach to the Synthesis of Amides

Kumar

et al. 2013

Eur J Org Chem

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Section: Resultsmentioning

confidence: 99%

Copper‐Catalyzed Oxidative Coupling of Carboxylic Acids with N,N‐Dialkylformamides: An Approach to the Synthesis of Amides

Kumar

et al. 2013

Eur J Org Chem

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“…The propagation entails addition of Me-NNTA onto the thiocarbamate chain end of the propagating macro-zwitterions 2 to form an acyclic thioanhydride intermediate 3 followed by an intramolecular skeletal rearrangement to form the secondary amide linkages accompanied by COS elimination ( Scheme 2 ). 44 , 45 This mechanism is akin to that proposed for the ring-opening polymerization of amino acid derived NCAs using aprotic initiators (e.g., pyridine or NaOMe) where a carbamate propagating species was invoked. 23 , 46 Our proposed mechanism for the TMG-mediated polymerization of Me-NNTA is based on the following considerations.…”

Section: Resultsmentioning

confidence: 98%

1,1,3,3-Tetramethylguanidine-Mediated Zwitterionic Ring-Opening Polymerization of Sarcosine-Derived N-Thiocarboxyanhydride toward Well-Defined Polysarcosine

et al. 2022

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Zwitterionic ring-opening polymerization (ZROP) of sarcosine-derived N- thiocarboxyanhydrides (Me-NNTAs) can be induced by using 1,1,3,3-tetramethylguanidine (TMG) initiators in CH 2 Cl 2 at 25 °C, rapidly producing well-defined polysarcosine polymers with controlled molecular weights ( M n = 1.9–37 kg/mol) and narrow molecular weight distributions ( Đ = 1.01–1.12). The reaction exhibits characteristics of a living polymerization, evidenced by pseudo-first-order polymerization kinetics, the linear increase of polymer molecular weight ( M n ) with conversion, and the successful chain extension experiments. The polymerization is proposed to proceed via propagating macro-zwitterions bearing a cationic 1,1,3,3-tetramethylguanidinium and an anionic thiocarbamate chain end. The TMG not only initiates the polymerization but also serves to stabilize the thiocarbamate chain end where the monomer addition occurs. Because of the enhanced hydrolytic stability of Me-NNTA, the polymerization can be conducted without the rigorous exclusion of moisture, further enhancing the appeal of the method to access well-defined polysarcosine.

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“…The subsequent chain propagation occurs by ring-opening addition of Bu-NCAs with the carbamate species followed by decarboxylation of the mixed anhydride intermediate (Scheme S1). Early studies of small molecular compounds revealed that the mixed anhydride linkages are kinetically labile, readily yielding amide linkages accompanied by CO 2 liberation. − …”

Section: Resultsmentioning

confidence: 99%

1,1,3,3-Tetramethylguanidine-Promoted Ring-Opening Polymerization of N-Butyl N-Carboxyanhydride Using Alcohol Initiators

et al. 2016

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N-Butyl N-carboxyanhydride (Bu-NCA) was polymerized in THF to produce poly(N-butylglycine) using benzyl alcohol initiator and 1,1,3,3-tetramethylguanidine (TMG) promoter. Poly(N-butylglycine) species (PNBG) with controlled molecular weight (M n = 2.9−20.5 kg mol −1 ) and narrow molecular weight distribution (PDI = 1.04−1.08) were obtained by controlling the initial monomer-to-initiator ratio and conversion. The reaction exhibits characteristics of a living polymerization, as evidenced by the linear increase of M n with conversion and successful chain extension experiments. Kinetic studies revealed a first-order dependence of propagation rate on the monomer and benzyl alcohol concentration and zero-order dependence on the TMG concentration, consistent with a controlled polymerization where the TMG does not influence the chain propagation. It was further revealed that the polymerization activities and M n control are strongly dependent on the structure of the alcohol initiators. Primary alcohols (e.g., methanol, ethanol, 2-methoxyethanol, npropanol, and benzyl alcohol) can mediate the polymerization of Bu-NCA with the TMG present to produce PNBG polymers with good to moderate control of M n s and PDIs. By contrast, sterically hindered secondary or tertiary alcohols (e.g., isopropyl alcohol and tert-butyl alcohol) or a primary alcohol bearing strongly electron withdrawing substituents (e.g., 2,2,2trifluoroethanol) or phenol either failed to initiate the polymerization or produced PNBGs whose molecular weights deviated to varying extents from the theoretical values based on single-site initiation with alcohols. 1 H NMR analysis revealed hydrogen bonding interactions between TMG and various alcohols, thereby promoting the initiation by enhancing the nucleophilicity of the alcohols toward ring-opening addition of Bu-NCA monomer. Electron-rich primary alcohols can initiate the polymerization more efficiently than the electron-deficient primary alcohol or sterically hindered secondary or tertiary alcohols, resulting in enhanced control over polymer molecular weight in the former than the latter. The polymerization has been successfully extended toward the synthesis of heteroblock copolymers based on poly(ethylene glycol) (PEG) and PNBG by using a hydroxylended PEG macroinitiator and TMG promoter.

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Peroxyester reaction of dimethylformamide

Cited by 17 publications

References 9 publications

Copper‐Catalyzed Oxidative Coupling of Carboxylic Acids with N,N‐Dialkylformamides: An Approach to the Synthesis of Amides

Copper‐Catalyzed Oxidative Coupling of Carboxylic Acids with N,N‐Dialkylformamides: An Approach to the Synthesis of Amides

1,1,3,3-Tetramethylguanidine-Mediated Zwitterionic Ring-Opening Polymerization of Sarcosine-Derived N-Thiocarboxyanhydride toward Well-Defined Polysarcosine

1,1,3,3-Tetramethylguanidine-Promoted Ring-Opening Polymerization of N-Butyl N-Carboxyanhydride Using Alcohol Initiators

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