Ruthenium catalyzed selective synthesis of enol carbamates by fixation of carbon dioxide

Mitsudo, Take‐aki; Hori, Yoji; Yamakawa, Yasushi; Watanabe, Yoshihisa

doi:10.1016/s0040-4039(00)96526-2

Cited by 126 publications

(67 citation statements)

References 5 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…1 Because 2-oxazolidones are versatile intermediates for the production of pharmaceuticals and fine chemicals and are also chiral auxiliaries, the CO 2 -based dehydrative carboxylation of amino alcohols, 2 the cycloaddition of aziridines 3 and the cyclization of alkynyl and alkenyl amines with CO 2 have been explored to construct the five-membered urethane ring structure. [4][5][6][7][8][9][10][11][12][13][14] These effective CO 2 fixation protocols are based on the conversion of thermodynamically less stable carbamic acids generated from amines and CO 2 into robust urethanes. 15 As a part of our research directed toward the development of addition reactions of CO 2 to unsaturated molecules, 14,16 we recently observed that N-heterocyclic carbene-coordinated Au(I) complexes effectively promote the carboxylative cyclization of propargylamines (1) under ambient CO 2 conditions to afford 5-vinylidene-2-oxazolidones (2) (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

Mechanistic Aspects of the Carboxylative Cyclization of Propargylamines and Carbon Dioxide Catalyzed by Gold(I) Complexes Bearing anN-Heterocyclic Carbene Ligand

2015

View full text Add to dashboard Cite

The carboxylative cyclization of a range of propargylic amines using carbon dioxide (CO 2 ) is promoted by IPr-gold(I) (IPr = 1,3-bis(2,6-diisopropylphenyl)-imidazol-2-ylidene) complexes to afford (Z)-5-alkylidene-2-oxazolidones in methanol under mild conditions, even in the absence of additives such as silver salts and bases. Investigation of the substrate scope shows that the catalytic performance is markedly retarded by the introduction of aromatic substituents at the alkyne terminus. The formation of alkenylgold(I) complexes as catalytic intermediate models is demonstrated by the treatment of methyl-and phenyl-substituted propargylamines with AuOH(IPr) under a CO 2 atmosphere. A comparison of the reactivity of the alkenylgold(I) complexes clearly indicates that the alkenyl ligand attached to an alkyl group at the  position is more susceptible to protonolysis compared with that attached to a phenyl group. These results and kinetic experiments corroborate a catalytic cycle that involves the nucleophilic attack of carbamate at the C-C triple bond bound to the Au center and its subsequent protodeauration to release the cyclic urethane products.

show abstract

Section: Introductionmentioning

confidence: 99%

Mechanistic Aspects of the Carboxylative Cyclization of Propargylamines and Carbon Dioxide Catalyzed by Gold(I) Complexes Bearing anN-Heterocyclic Carbene Ligand

2015

View full text Add to dashboard Cite

show abstract

“…A variety of protocols has been reported for the carboxylative cyclization reaction. Propargylic amines have reacted with CO 2 in the presence of organometallic complexes of ruthenium [2] and palladium. [3] Catalyst-free versions of the carboxylative cyclization of propargylamines with CO 2 have been achieved using strong bases, [4] in supercritical CO 2 , [5] and under electrochemical conditions.…”

mentioning

confidence: 99%

“…Propargylic amines have reacted with CO 2 in the presence of organometallic complexes of ruthenium [2] and palladium. [3] Catalyst-free versions of the carboxylative cyclization of propargylamines with CO 2 have been achieved using strong bases, [4] in supercritical CO 2 , [5] and under electrochemical conditions. [6] However, these protocols are often limited by high CO 2 pressure and/or restricted to propargylamines bearing terminal alkynes.…”

mentioning

confidence: 99%

Copper‐Catalyzed Four‐Component Coupling between Aldehydes, Amines, Alkynes, and Carbon Dioxide

Yoo

2008

Adv Synth Catal

129

View full text Add to dashboard Cite

show abstract

“…An important example of a binary catalyst system for the formation of these types of oxazolidinones was reported by Mitsudo [118] in 1987 using a Ru catalyst [i.e., (4-1,5-cyclooctadiene) (6-1,3, 5-cyclooctatriene)ruthenium] and a tertiary phosphine to give the 5-methylene-2-oxazolidinone products from N-substituted propargylamines and CO 2 in high yield and good regio-and stereoselectivity. In this context, Costa reported some interesting examples of unsaturated oxazolidinone formation in 1996 and 1999.…”

Section: Co 2 Coupling Reactions With Amino Alcohols and Propargylic mentioning

confidence: 99%

Metal Complexes Catalyzed Cyclization with CO2

Rintjema

Carrodeguas

Laserna

et al. 2015

Topics in Organometallic Chemistry

View full text Add to dashboard Cite

This chapter describes in general terms the catalytic methodology that has been made available for the use of carbon dioxide (CO 2 ) in cyclization reactions that incorporate an intact CO 2 fragment without changing the formal oxidation state of the carbon center. The major focus of this chapter will be on the most successful organometallic/inorganic complexes that have been used as catalyst systems throughout the last decade and the preferred ligand frameworks leading to elevated reactivity and/or selectivity behavior in CO 2 coupling reactions. Attention will be especially given to homogeneous catalyst systems as they have proven to be more versatile in CO 2 conversion catalysis and often have modular characteristics that allow for optimization of structure-activity relationships. The most important reactions that have been studied in the current context are designated CO 2 "addition" reactions to small molecule heterocycles such as epoxides and aziridines, though more recently other coupling partners such as diamines, dialcohols, and amino nitriles have further advanced the use of CO 2 in organic synthesis providing access to a wider range of structures. This chapter will serve to demonstrate the utility of CO 2 as a carbon reagent in the catalytic formation of the most prominent organic structures using cyclization strategies specifically.

show abstract

Ruthenium catalyzed selective synthesis of enol carbamates by fixation of carbon dioxide

Cited by 126 publications

References 5 publications

Mechanistic Aspects of the Carboxylative Cyclization of Propargylamines and Carbon Dioxide Catalyzed by Gold(I) Complexes Bearing anN-Heterocyclic Carbene Ligand

Mechanistic Aspects of the Carboxylative Cyclization of Propargylamines and Carbon Dioxide Catalyzed by Gold(I) Complexes Bearing anN-Heterocyclic Carbene Ligand

Copper‐Catalyzed Four‐Component Coupling between Aldehydes, Amines, Alkynes, and Carbon Dioxide

Metal Complexes Catalyzed Cyclization with CO2

Contact Info

Product

Resources

About