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Synfacts 2025; 21(01): 35
DOI: 10.1055/a-2467-5403
Metals in Synthesis

Iridium-Catalyzed Anti-Markovnikov Hydrocarboxylation of Olefins

Contributor(s):
Mark Lautens 
,
Alexa Torelli
Ghosh P, Maiti S, Malandain A, Raja D, Loreau O, Maity B, Roy TK, Audisio D *, Maiti D *. Université Paris Saclay, Gif-sur-Yvette, France and Indian Institute of Technology Bombay, Mumbai, India
Taming CO2•– via Synergistic Triple Catalysis in Anti-Markovnikov Hydrocarboxylation of Alkenes.

J. Am. Chem. Soc. 2024;
146: 30615-30625
DOI: 10.1021/jacs.4c12294
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Keywords

iridium catalysis - hydrocarboxylation - anti-Markovnikov

Significance

A photocatalyzed anti-Markovnikov hydrocarboxylation of terminal alkenes is reported. The success and utility of this methodology hinge on the controlled generation and maintenance of a low steady-state concentration of carbon dioxide radical anion species (CO₂•−). The authors demonstrate that this approach is compatible with various activated and unactivated alkenes, chiral scaffolds, and olefins containing competing 1,4-/5-/6-hydrogen atom transfer (HAT) sites.


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Comment

The authors propose that silyl formate A is generated via the reaction of Cs2CO3 with (TMS)₂SiH and CO₂, serving as a reservoir for formate. Upon UV irradiation, the iridium photocatalyst is excited, leading to the oxidation of DABCO, which then undergoes hydrogen atom abstraction (HAA) from A to produce the radical anion species B. Species B then reacts with the alkene in an anti-Markovnikov manner, and subsequent quenching by tris(trimethylsilyl)silane yields the product.


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Publication History

Article published online:
20 December 2024

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