Chiral N,N Ligands Enabling Palladium‐Catalyzed Enantioselective Intramolecular Heck–Matsuda Carbonylation Reactions by Sequential Migratory and CO Insertions

Carmona, Rafaela C.; Köster, Otto D.; Correia, Carlos Roque Duarte

doi:10.1002/ange.201805831

Cited by 36 publications

(9 citation statements)

References 84 publications

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“…In 2018, we reported the first enantioselective intramolecular exocarbonylative Heck-Matsuda reaction, employing chiral N,N ligands (Scheme 1a). [10] In line with this work, Kong and coworkers reported the enantioselective double Heck reaction, [11] an intramolecular Heck-Matsuda reaction followed by an intermolecular Heck using the same substrate previously reported by us (Scheme 1a). Another potential reason for the slow development of the Heck-Matsuda reactions is a general perception, to some extent reasonable, that arenediazonium salts are potentially hazardous compounds for use in organic synthesis, especially on a large scale, although tetrafluoroborates, tosylates, and hexafluorophosphates diazonium salts are usually thermally stable compounds.…”

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confidence: 70%

“…Compound 8 was obtained as a single diastereoisomer (stereochemistry was determined by NOESY, see SI). The successful results obtained with the in tandem enantioselective Heck-Matsuda reactions using the unsaturated anilines have motivated us to briefly reinvestigate the enantioselective carbonylative reactions disclosed in 2018, [10] including some anilines from which the respective aryldiazonium salt proved extremely difficult to synthesize. In this case, due to the quite distinct reaction conditions needed for efficient carbonylations, another optimization study was carried out (see SI).…”

Section: Table 3 Reaction Scope For the Synthesis Of Methanobenzo[b]o...mentioning

confidence: 99%

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In Tandem Enantioselective Intramolecular Heck-Matsuda Reactions directly from anilines

Correia

Chorro

Souza

et al. 2022

Preprint

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A new enantioselective intramolecular strategy for the synthesis of enantioenriched bridged benzoxacines, unsaturated spirobenzofurans, methyl-2,3-dihydrobenzofuran acetates, and methyl-2,3-indoline acetate scaffolds in a tandem-like diazotization/Heck Matsuda process directly from anilines has been developed. The process combines the in situ diazotization of the aniline, followed by the intramolecular Heck-Matsuda reaction, thus skipping the isolation and purification of unstable or hard-to-synthesize aryldiazonium salts. The practicality and robustness of the sequence were demonstrated by the synthesis of 26 examples of complex structural motifs with yields up to 91% and enantiomeric ratio (er) up to 97:3, including quaternary stereocenters. The in-tandem processes from anilines were compared to conventional Heck Matsuda reactions using pre-synthesized aryldiazonium salts. With few exceptions, the reactions starting directly from the anilines afforded better overall yields and er, demonstrating the efficiency of this method.

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confidence: 70%

Section: Table 3 Reaction Scope For the Synthesis Of Methanobenzo[b]o...mentioning

confidence: 99%

In Tandem Enantioselective Intramolecular Heck-Matsuda Reactions directly from anilines

Correia

Chorro

Souza

et al. 2022

Preprint

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“…The successful results obtained with the in tandem enantioselective Heck‐Matsuda reactions directly from the unsaturated anilines have motivated us to briefly reinvestigate the enantioselective carbonylative reactions disclosed in 2018, [10] including some anilines from which the respective aryldiazonium salt proved difficult to synthesize. In this case, due to the quite distinct reaction conditions needed for efficient carbonylations, another optimization study was carried out (see SI).…”

Section: Methodsmentioning

confidence: 99%

In Tandem Enantioselective Intramolecular Heck‐Matsuda Reactions directly from Anilines

et al. 2023

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A new enantioselective intramolecular strategy for the synthesis of enantioenriched bridged benzoxacines, unsaturated spirobenzofurans, 2,3‐dihydrobenzofuran and 2,3‐indoline acetate scaffolds in a tandem‐like diazotization/Heck‐Matsuda process directly from anilines has been developed. The process combines the in situ diazotization of the aniline, followed by the intramolecular Heck‐Matsuda reaction, thus skipping the isolation and purification of potentially unstable or hard‐to‐synthesize aryldiazonium salts. The practicality and robustness of the sequence were demonstrated by the synthesis of 30 complex motifs in yields up to 91% and enantiomeric ratios up to 97:3, including quaternary stereocenters. The in‐tandem processes from anilines were compared to conventional Heck‐Matsuda reactions using pre‐synthesized aryldiazonium salts. With few exceptions, the reactions starting directly from the anilines afforded better overall yields and enantioselectivity, demonstrating the efficiency of the method.

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“…In 2018, we reported the first enantioselective intramolecular exocarbonylative Heck reaction through the combination of arenediazonium salts and N,N ‐chiral ligands to generate enantioenriched dihydrobenzofurans under mild and operationally simple reaction conditions (Scheme 18). [60] Under palladium catalysis and CO atmosphere, several enantioenriched dihydrobenzofurans 112 and 113 were obtained in up to 96 % ee . Notably, this Heck‐Matsuda transformation was the first enantioselective example where carbonylative Heck reactions proceeded through a sequence involving as its first step a migratory insertion, followed by CO insertion.…”

Section: The Enantioselective Intramolecular Heck‐matsuda Reactionmentioning

confidence: 99%

Enantioselective Heck‐Matsuda Reactions: From Curiosity to a Game‐Changing Methodology

Oliveira

Correia

2021

The Chemical Record

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The enantioselective palladium‐catalyzed Heck arylation of olefins using arenediazonium salts is one of the last features in the evolution of a synthetic method known as the Heck‐Matsuda reaction. This personal account highlights the development of the enantioselective Heck‐Matsuda reaction in its initial stages, the challenges faced along the way, and the interesting findings that opened new synthetic opportunities, mainly from our laboratory, featuring the Heck‐Matsuda reaction as a central player in the synthesis of bioactive and functional molecules.

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Chiral N,N Ligands Enabling Palladium‐Catalyzed Enantioselective Intramolecular Heck–Matsuda Carbonylation Reactions by Sequential Migratory and CO Insertions

Cited by 36 publications

References 84 publications

In Tandem Enantioselective Intramolecular Heck-Matsuda Reactions directly from anilines

In Tandem Enantioselective Intramolecular Heck-Matsuda Reactions directly from anilines

In Tandem Enantioselective Intramolecular Heck‐Matsuda Reactions directly from Anilines

Enantioselective Heck‐Matsuda Reactions: From Curiosity to a Game‐Changing Methodology

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