Recent advances in the transition metal catalyzed carbonylation of alkynes, arenes and aryl halides using CO surrogates

Gautam, Prashant; Bhanage, Bhalchandra M.

doi:10.1039/c5cy00691k

Cited by 244 publications

(83 citation statements)

References 132 publications

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“…The field of non‐gaseous carbonylation reactions has flourished over the last decade with the development of several novel CO sources that have eradicated the need to use cumbersome CO gas . The main focus has been to identify and develop cheap, easy to handle and convenient reagents that can be used for carbonylations, including isotopic labeling.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of 4H‐Benzo[e][1,3]oxazin‐4‐ones by a Carbonylation–Cyclization Domino Reaction of ortho‐Halophenols and Cyanamide

et al. 2017

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A mild and convenient one‐step preparation of 4H‐1,3‐benzoxazin‐4‐ones by a domino carbonylation–cyclization process is developed. Readily available ortho‐iodophenols are subjected to palladium‐catalyzed carbonylative coupling with Mo(CO)6 and cyanamide, followed by a spontaneous, intramolecular cyclization to afford 4H‐1,3‐benzoxazin‐4‐ones in moderate to excellent yields. Furthermore, the scope of the reaction is extended to include challenging ortho‐bromophenols. Finally, to highlight the versatility of the developed method, Mo(CO)6 is successfully replaced with a wide array of CO‐releasing reagents, such as oxalyl chloride, phenyl formate, 9‐methylfluorene‐9‐carbonyl chloride, and formic acid, making this an appealing strategy for the synthesis of 4H‐benzo[e][1,3]oxazin‐4‐ones.

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Section: Resultsmentioning

confidence: 99%

Synthesis of 4H‐Benzo[e][1,3]oxazin‐4‐ones by a Carbonylation–Cyclization Domino Reaction of ortho‐Halophenols and Cyanamide

et al. 2017

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“…Nonetheless, a drawback to this otherwise valuable C1‐building block is its safety concerns, as exposure to the gas can lead to asphyxiation. Due to this and the reluctance to handle pressurized bottles, there has been a significant interest in recent years to develop CO‐releasing molecules (CORMs) to circumvent such obstacles . Importantly, all of the developed procedures applying either high‐pressure CO from autoclaves or low‐pressure CO generation from CORMs can readily be adapted to the use of [ 13 C ]CO.…”

Section: Introductionmentioning

confidence: 99%

Recent developments in carbonylation chemistry using [¹³C]CO, [¹¹C]CO, and [¹⁴C]CO

Nielsen

Neumann

Lindhardt

et al. 2018

Labelled Comp Radiopharmac

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Carbon monoxide represents the most important C1-building block for the chemical industry, both for the production of bulk and fine chemicals, but also for synthetic fuels. Yet its toxicity and subsequently its cautious handling have limited its applications in medicinal chemistry research and in particular for the synthesis of pharmaceutically relevant molecules. Recent years have nevertheless witnessed a considerable headway on the development of carbon monoxide surrogates and reactor systems, which provide an ideal setting for performing carbonylation chemistry with stoichiometric and substoichiometric carbon monoxide. Such setups are particularly ideal for the introduction of isotope labels such as carbon-11, carbon-13, and carbon-14 into bioactive compounds. This review summarizes this growing field and examines the large number of carbonylation reactions that can be exploited for the introduction of a carbon isotope.

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“…[24][25][26][27] We recently reported a series of external-CO-free carbonylation of haloarenes utilizing phenyl formate or other formic acid derivatives as CO surrogates.…”

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confidence: 99%

“…[24][25][26][27] We recently reported a series of external-CO-free carbonylation of haloarenes utilizing phenyl formate or other formic acid derivatives as CO surrogates. [28][29][30][31][32] These CO surrogates can generate CO under mild conditions in a closed reaction vessel, and this CO is consumed during carbonylation in a highly safe and efficient manner.…”

mentioning

confidence: 99%

Practical Synthesis of Axially Chiral Dicarboxylates <i>via</i> Pd-Catalyzed External-CO-Free Carbonylation

Konishi

Hoshino

Manabe

2016

CHEMICAL & PHARMACEUTICAL BULLETIN

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We have developed a safe and practical synthetic method for preparing axially chiral diphenyl dicarboxylates using Pd-catalyzed external-CO-free carbonylation with phenyl formate as a CO surrogate. Optimized conditions consisted of axially chiral [1,1′-binaphthalene]-2,2′-diyl ditriflate and its congeners, each easily prepared from commercially available enantiomerically pure diols, Pd(OAc) 2 , 1,3-bis(diphenylphosphino)-propane, ethyldiisopropylamine, and no solvent. To demonstrate the potential utility of these products, this method was conducted on gram-scale and the phenyl ester products were converted to other useful compounds, and both processes were carried out without difficulty.Key words axially chiral dicarboxylate; carbonylation; phenyl formate; carbon monoxide surrogate; palladium; catalysis Axially chiral compounds have found wide applications as ligands and organocatalysts in asymmetric organic reactions.1-5) Their chiral backbones effectively construct an asymmetric environment around the molecules, enabling catalytic transformations, often with high enantioselectivity. A number of biaryl and spirocyclic chiral ligands are commercially available from multiple suppliers, and many recent papers mentioning the development of novel axially chiral ligands and organocatalysts indicate increasing demand and potential of axially chiral compounds for asymmetric catalysis.In the search for highly effective chiral ligands and organocatalysts, [1,1′-binaphthalene]-2,2′-dicarboxylic acid and its derivatives such as esters are attractive axially chiral compounds.6-9) However, most previous methods for the synthesis of the enantiomerically pure dicarboxylic acid and dicarboxylates required multiple tedious steps. [10][11][12][13][14][15][16][17] In addition, many of the methods include time-consuming optical resolution of racemic dicarboxylic acid. Therefore, it is desirable to develop more practical synthetic methods with fewer steps. Since enantiomerically pure 1,1′-bi-2-naphthol is readily available from many suppliers, it would be an efficient starting point in the synthesis of the targeted dicarboxylates (Chart 1). Recently, Hamashima and colleagues reported the synthesis of dicarboxylic acid from 1,1′-bi-2-naphthol via lithiation of [1,1′-binaphthalene]-2,2′-diyl diphosphate followed by carboxylation with carbon dioxide.18) While this method affords dicarboxylic acid in high yield in two steps, the involvement of the strongly basic dilithiated intermediate might prove unmanageable with more complex substrates. As another route to [1,1′-binaphthalene]-2,2′-dicarboxylates from 1,1′-bi-2-naphthol, Takaya and colleagues previously reported the Pd-catalyzed alkoxycarbonylation of [1,1′-binaphthalene]-2,2′-diyl ditriflate using carbon monoxide (CO) gas. 19) Proving the utility of this pioneering work, many other researchers have used this method to obtain various derivatives. [20][21][22][23] While this method gives dicarboxylates in good yield under relatively mild, weakly basic conditions, use of the highly to...

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Recent advances in the transition metal catalyzed carbonylation of alkynes, arenes and aryl halides using CO surrogates

Abstract: Transition metal catalyzed carbonylation reactions using carbon monoxide as the C-1 source have occupied an all important position in catalysis which is subsequently related to organic synthesis and industrial synthesis of molecules.

Cited by 244 publications

References 132 publications

Synthesis of 4H‐Benzo[e][1,3]oxazin‐4‐ones by a Carbonylation–Cyclization Domino Reaction of ortho‐Halophenols and Cyanamide

Synthesis of 4H‐Benzo[e][1,3]oxazin‐4‐ones by a Carbonylation–Cyclization Domino Reaction of ortho‐Halophenols and Cyanamide

Recent developments in carbonylation chemistry using [¹³C]CO, [¹¹C]CO, and [¹⁴C]CO

Practical Synthesis of Axially Chiral Dicarboxylates <i>via</i> Pd-Catalyzed External-CO-Free Carbonylation

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Recent advances in the transition metal catalyzed carbonylation of alkynes, arenes and aryl halides using CO surrogates

Abstract: Transition metal catalyzed carbonylation reactions using carbon monoxide as the C-1 source have occupied an all important position in catalysis which is subsequently related to organic synthesis and industrial synthesis of molecules.

Cited by 244 publications

References 132 publications

Synthesis of 4H‐Benzo[e][1,3]oxazin‐4‐ones by a Carbonylation–Cyclization Domino Reaction of ortho‐Halophenols and Cyanamide

Synthesis of 4H‐Benzo[e][1,3]oxazin‐4‐ones by a Carbonylation–Cyclization Domino Reaction of ortho‐Halophenols and Cyanamide

Recent developments in carbonylation chemistry using [13C]CO, [11C]CO, and [14C]CO

Practical Synthesis of Axially Chiral Dicarboxylates <i>via</i> Pd-Catalyzed External-CO-Free Carbonylation

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Recent developments in carbonylation chemistry using [¹³C]CO, [¹¹C]CO, and [¹⁴C]CO