Recent Advances on Diverse Decarboxylative Reactions of Amino Acids

Rahman, Matiur; Mukherjee, Anindita; Коvalev, Igor S.; Kopchuk, Dmitry S.; Zyryanov, Grigory V.; Tsurkan, Mikhail V.; Majee, Adinath; Ranu, Brindaban C.; Charushin, Valery N.; Чупахин, О. Н.

doi:10.1002/adsc.201801331

Cited by 75 publications

(26 citation statements)

References 295 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Within the last two decades, a rapidly growing number of decarboxylative functionalization reactions have been disclosed based on these concepts. Most decarboxylative C−C couplings are covered by recent reviews, [7–29] but decarboxylative reactions with the formation of C‐heteroatom bonds are only considered on the sideline or limited to discussion on one specific C‐heteroatom bond [30–35] . Hence, this review aims at providing a comprehensive overview of decarboxylative heterofunctionalization, especially highlighting the progress made within the last decade until January 2021 (Scheme 2).…”

Section: Introductionmentioning

confidence: 99%

Decarboxylation‐Initiated Intermolecular Carbon‐Heteroatom Bond Formation

Zeng¹,

Feceu

Sivendran

et al. 2021

Adv Synth Catal

View full text Add to dashboard Cite

Carboxylic acids are among the most used feedstock chemicals due to their great structural diversity and easy handling. The use of carboxylic acids and their derivatives in decarboxylative couplings has proven to be a valuable tool for the construction of C−C and C‐heteroatom bonds. This synthetic strategy provides a complementary bond disconnection to traditional cross‐coupling methods. In this review, we provide a comprehensive overview of decarboxylation‐initiated intermolecular C‐heteroatom bond formation, outlining several main mechanistic concepts combined with early examples and highlighting the achievements made in the past decade until January 2021. In these reactions, carboxylic acids and their derivatives undergo initial decarboxylation and then react with other heteroatom electrophiles and nucleophiles, thus replacing the carboxylate group with a valuable and prevalent heteroatom functionality.

show abstract

Section: Introductionmentioning

confidence: 99%

Decarboxylation‐Initiated Intermolecular Carbon‐Heteroatom Bond Formation

Zeng¹,

Feceu

Sivendran

et al. 2021

Adv Synth Catal

View full text Add to dashboard Cite

show abstract

“…The chloromethyl radical generation by photoredox catalysis is a useful strategy for cyclopropanation [58]. Most photoredox catalyzed, decarboxylative generations of carbon-centered radicals are based on the formation of "stabilized" α-amino [59][60][61][62][63][64][65] or benzyl [66][67][68][69][70] radical species. However, the generation of unstabilized alkyl radical species is also known [71][72][73][74].…”

Section: Resultsmentioning

confidence: 99%

Visible-light-induced addition of carboxymethanide to styrene from monochloroacetic acid

Vliet¹,

Leeuwen²,

Brouwer³

et al. 2020

Beilstein J. Org. Chem.

View full text Add to dashboard Cite

Where monochloroacetic acid is widely used as a starting material for the synthesis of relevant groups of compounds, many of these synthetic procedures are based on nucleophilic substitution of the carbon chlorine bond. Oxidative or reductive activation of monochloroacetic acid results in radical intermediates, leading to reactivity different from the traditional reactivity of this compound. Here, we investigated the possibility of applying monochloroacetic acid as a substrate for photoredox catalysis with styrene to directly produce γ-phenyl-γ-butyrolactone. Instead of using nucleophilic substitution, we cleaved the carbon chlorine bond by single-electron reduction, creating a radical species. We observed that the reaction works best in nonpolar solvents. The reaction does not go to full conversion, but selectively forms γ-phenyl-γ-butyrolactone and 4-chloro-4-phenylbutanoic acid. Over time the catalyst precipitates from solution (perhaps in a decomposed form in case of fac-[Ir(ppy)3]), which was proven by mass spectrometry and EPR spectroscopy for one of the catalysts (N,N-5,10-di(2-naphthalene)-5,10-dihydrophenazine) used in this work. The generation of HCl resulting from lactone formation could be an additional problem for organometallic photoredox catalysts used in this reaction. In an attempt to trap one of the radical intermediates with TEMPO, we observed a compound indicating the generation of a chloromethyl radical.

show abstract

“…Despite significant experimentation, less activated amines such as pyrrolidine and piperidine did not participate in redox-annulations with ortho -(nitromethyl)benzaldehyde ( 1a ). However, as has been shown in a number of related reactions, 15 , 16 the corresponding decarboxylative reactions in which proline and pipecolic acid are used in place of pyrrolidine and piperidine provided annulation products in good yields ( Scheme 6 ). Denitration under Carreira conditions was also successful.…”

mentioning

confidence: 80%

Traceless Redox-Annulations of Alicyclic Amines

Rickertsen

Paul

et al. 2020

SynOpen

View full text Add to dashboard Cite

Amines such as 1,2,3,4-tetrahydroisoquinoline undergo redox-neutral annulations with ortho-(nitromethyl)benzaldehyde. Benzoic acid acts as a promoter in these reactions, which involve concurrent amine α-C–H bond and N–H bond functionalization. Subsequent removal of the nitro group provides access to tetrahydroprotoberberines not accessible via typical redox-annulations. Also reported are decarboxylative annulations of ortho-(nitromethyl)benzaldehyde with proline and pipecolic acid.

show abstract

Recent Advances on Diverse Decarboxylative Reactions of Amino Acids

Cited by 75 publications

References 295 publications

Decarboxylation‐Initiated Intermolecular Carbon‐Heteroatom Bond Formation

Decarboxylation‐Initiated Intermolecular Carbon‐Heteroatom Bond Formation

Visible-light-induced addition of carboxymethanide to styrene from monochloroacetic acid

Traceless Redox-Annulations of Alicyclic Amines

Contact Info

Product

Resources

About