Ligand‐ and Solvent‐Controlled Regio‐ and Chemodivergent Carbonylative Reactions

Geng

2019

Chem

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468

170

Carbon monoxide is one of the most important C1 molecules in organic chemistry. Many novel procedures for its conversion have been developed, and some have even been industrialized. In this review, we discuss and categorize CO chemistry into four classes: (1) transition-metal-mediated carbonylation, (2) strong-acid-initiated cationic carbonylation, (3) anionic carbonylation, and (4) free-radical carbonylation. Relevant achievements are selected and discussed in detail.

Section: Transition-metal-mediated Carbonylation Reactionsmentioning

confidence: 99%

The Chemistry of CO: Carbonylation

Geng

2019

Chem

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468

170

“…[1][2][3][4] On the other hand, selectivity controlledt ransformations can proliferate the products obtainable from the same substrates. [5][6][7][8] It is especially interesting that the selectivity of the products is tuned by slightly modifying the catalyst system.…”

mentioning

confidence: 99%

Palladium‐Catalyzed Tunable Carbonylative Synthesis of Enones and Benzofulvenes

Spannenberg

et al. 2019

Chemistry A European J

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Ap alladium-catalyzed four-component carbonylative coupling reaction involving aryl halides, internal alkynes, arylboronic acids, and CO has been developedf or the first time.A ll-carbon substituted a-unsaturated ketones and benzofulvenes can be selectively obtained in a highly regio-and stereocontrolled manner.U sing Cu(TFA) 2 as the additive, as eries of tetrasubstituted a-unsaturated ketonesw ere prepared in moderate to high yields. Using more acidic Lewis acid Cu(OTf) 2 as the additive, multisubstitutedb enzofluvenes were synthesized in moderate yields. This efficient methodology involved the formation of three new CÀCb onds, and provided ad ivergent methodf or the quick construction of multisubstituted aunsaturated ketones and benzofulvenes from easily available starting materials.Scheme1.Carbonylative synthesis of tetrasubstituted enones.[a] Dr.Supporting information and the ORCID identification number(s) for the author(s) of this articlecan be found under: https://doi.

“…A series of phosphine ligands were also examined to determine the ligand effect on this transformation (Table 1, entries 9-11, see details in SI). [16] Bidentate phosphine ligands showed lower activity, the yields decreased to 42% and 2% for dppf and xantphos respectively. Monodentate phosphine ligands such as trianisylphosphine were effective to catalyze this reaction and provided the product 3 gb in comparable yield.…”

Section: Resultsmentioning

confidence: 96%

Palladium‐Catalyzed Carbonylative Coupling of Aryl Iodides with Alkyl Bromides: Efficient Synthesis of Alkyl Aryl Ketones

Chen

et al. 2018

Adv Synth Catal

Alkyl aryl ketones are important structures with applications in many areas of chemistry. Hence, efficient procedures for their production are particularly attractive. In this communication, a general and efficient carbonylative cross-coupling of aryl iodides and unactivated alkyl bromides is presented. By using a simple palladium catalyst, a series of alkyl aryl ketones were synthesized in moderate to excellent yields from readily available alkyl and aryl halides in an In-Ex tube with formic acid as the CO source. In this study both primary and secondary alkyl bromides/iodides were suitable coupling partners. Additionally, this method can also be employed for the late-stage functionalization of complex natural products and polyfunctionalized molecules.