Selective deuteration of (hetero)aromatic compounds via deutero-decarboxylation of carboxylic acids

Grainger, Rachel; Nikmal, Arif; Cornellà, Josep; Larrosa, Igor

doi:10.1039/c2ob25157d

Cited by 50 publications

(27 citation statements)

References 36 publications

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“…1% each) and used an internal standard. 29 This allowed for an extremely accurate measurement of the 2 H KIEs. Two independent experiments ( Figure 1 b, black) showed an inverse KIE at C-3 (0.87 ± 0.01, 0.88 ± 0.01) and no KIE at C-2 (1.02 ± 0.01, 1.00 ± 0.01).…”

Section: Resultsmentioning

confidence: 99%

Room-Temperature Direct β-Arylation of Thiophenes and Benzo[b]thiophenes and Kinetic Evidence for a Heck-type Pathway

et al. 2016

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The first example of a regioselective β-arylation of benzo[b]thiophenes and thiophenes at room temperature with aryl iodides as coupling partners is reported. This methodology stands out for its operational simplicity: no prefunctionalization of either starting material is required, the reaction is insensitive to air and moisture, and it proceeds at room temperature. The mild conditions afford wide functional group tolerance, often with complete regioselectivity and high yields, resulting in a highly efficient catalytic system. Initial mechanistic studies, including 13C and 2H KIEs, suggest that this process occurs via a concerted carbo-palladation across the thiophene double bond, followed by a base-assisted anti-elimination.

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Section: Resultsmentioning

confidence: 99%

Room-Temperature Direct β-Arylation of Thiophenes and Benzo[b]thiophenes and Kinetic Evidence for a Heck-type Pathway

et al. 2016

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“…Furthermore, deuterodecarboxylation can be a highly selective method to deuterium label (hetero)arenes. 80 Protodecarboxylation is thought to occur via a two-step mechanism: (i) decarboxylation from a metal-carboxylate to form a metal-aryl complex and (ii) protonation of the metal-aryl complex (Scheme 11). Subtle differences have been reported in the decarboxylation step for copper (Scheme 12A) and silver (not shown) relative to palladium (Scheme 12B).…”

Section: Scheme 11 Protodecarboxylationmentioning

confidence: 99%

Aryl-Decarboxylation Reactions Catalyzed by Palladium: Scope and Mechanism

Daley¹,

Topczewski

2019

Synthesis

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Palladium-catalyzed cross-couplings and related reactions have enabled many transformations essential to the synthesis of pharmaceuticals, agrochemicals, and organic materials. A related family of reactions that have received less attention are decarboxylative functionalization reactions. These reactions replace the preformed organometallic precursor (e.g., boronic acid or organostannane) with inexpensive and readily available carboxylic acids for many palladium-catalyzed reactions. This review focuses on catalyzed reactions where the elementary decarboxylation step is thought to occur at a palladium center. This review does not include decarboxylative reactions where decarboxylation is thought to be facilitated by a second metal (copper or silver) and is specifically limited to (hetero)arenecarboxylic acids. This review includes a discussion of oxidative Heck reactions, protodecarboxylation reactions, and cross-coupling reactions among others.1 Introduction2 Oxidative Heck Reactions3 Protodecarboxylation Reactions4 Cross-Coupling Reactions5 Other Reactions6 Conclusion

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“…2009 年, Larrosa 等 [84] 发展了一种以碳酸银作氧化剂、以乙酸作为质子源、以二甲基亚砜作溶剂的选择性脱羧反应. 经过进一步的研究, 2012 年, 该课题组 [85] [87] 探究了钴催化的芳香族化合物脱卤化的机理. 2014 年, 王健吉等 [88] 用乙酰丙酮钴作催化剂, 以四氢铝锂作还原剂实现了醚键断裂(表 1).…”

Section: 银催化的去官能团化反应unclassified

Recent Advances in Transition-Metal Catalyzed Defunctionalization Reaction

Dong¹,

Jin²,

Liu³

2020

Chin. J. Org. Chem.

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Functional groups are atoms or groups that determine the chemical properties of organic compounds. It often plays the role of guiding group in organic synthesis chemistry. Defunctionalization is the chemical transformation of a substrate with more functional groups into a compound with fewer functional groups, which has positive applications in solving environmental problems, resource shortage and biomass degradation. But due to the bond energy, heating, acid or base are often involved in defunctionalization. In recent years, defunctionalization has been moving toward a greener and more sustainable direction. Metal catalysis provides a new way for defunctionalization. The recent applications of different metalmediated defunctionalization in organic synthesis and their mechanism are summarized.

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Selective deuteration of (hetero)aromatic compounds via deutero-decarboxylation of carboxylic acids

Cited by 50 publications

References 36 publications

Room-Temperature Direct β-Arylation of Thiophenes and Benzo[b]thiophenes and Kinetic Evidence for a Heck-type Pathway

Room-Temperature Direct β-Arylation of Thiophenes and Benzo[b]thiophenes and Kinetic Evidence for a Heck-type Pathway

Aryl-Decarboxylation Reactions Catalyzed by Palladium: Scope and Mechanism

Recent Advances in Transition-Metal Catalyzed Defunctionalization Reaction

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