Asymmetric Catalysis with CO<sub>2</sub>:  Direct Synthesis of Optically Active Propylene Carbonate from Racemic Epoxides

Lu, Xiao‐Bing; Liang, Bin; Zhang, Yin-Ju; Tian, Ye; Wang, Yiming; Bai, Chenxi; Wang, Hui; Zhang, Rong

doi:10.1021/ja049734s

Cited by 346 publications

(173 citation statements)

References 29 publications

(19 reference statements)

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“…under extremely mild and solvent-free conditions. 99 Unfortunately the kinetic resolution coefficients measured (k rel < 10) were still far from being optimal compared with wellknown hydrolytic kinetic resolution methods. 100 More recently, the same group reported a multichiral Co(III) complexes 22 ( Figure 9) which was used in conjuction with the 2,4-dinitrophenolate salt of PPN (PPN-DNP) as the nucleophilic co-catalyst.…”

Section: Methodsmentioning

confidence: 99%

Recent Advances in the Catalytic Preparation of Cyclic Organic Carbonates

2015

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ABSTRACT:The catalytic formation of cyclic organic carbonates (COCs) using carbon dioxide (CO 2 ) as a renewable carbon feed stock is a highly vibrant area of research with an increasing amount of researchers focusing on this thematic investigation. These organic carbonates are highly useful building blocks and nontoxic reagents, and are most commonly derived from CO 2 coupling reactions with oxirane and di-alcohol precursors using homogeneous catalysis methodologies. The activation of suitable reaction partners using catalysis as a key technology is a requisite for efficient CO 2 conversion as its high kinetic stability poses a barrier to access functional organic molecules with added value in both academic and industrial laboratories. Though this area of science has been flourishing for at least a decade, in the last 2−3 years significant advancements have been made to address the general reactivity and selectivity issues that are associated with the formation of COCs. Here we present a concise overview of these activities with a primary focus to highlight the most important progress made and the opportunities that catalysis can bring about when the synthesis of these intermediates is optimized to a higher level of sophistication. The attention will be limited to those cases where homogeneous metal-containing systems have been employed as they possess the highest potential for directed organic synthesis using CO 2 as molecular building block. This review discusses examples of exceptional reactivity and selectivity taking into account the challenging nature of the substrates that were involved, and mechanistic understanding guiding the optimization of these protocols is also highlighted.

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Section: Methodsmentioning

confidence: 99%

Recent Advances in the Catalytic Preparation of Cyclic Organic Carbonates

2015

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“…Notably, the chiral Lewis base did not contribute significantly to the enantioselectivity. Later, Lu reported the use of a similar cobalt(III)salen complex 4 in the presence of two equivalents of n-NBu 4 Cl (n-tetrabutylammonium chloride) for the synthesis of enantioenriched propylene carbonate 2a [11]. The bulky p-toluene-sulfonate counterion was essential to obtain high enantioselectivity.…”

Section: Cobalt(iii) Salen Complexesmentioning

confidence: 99%

“…Although a number of metal-based salen complexes have been developed [11,18] only a few catalytic systems gave comparable results to that of cobalt-based complexes. Recently, North et al have reported the use of aluminium(III) and chromium(III) salen complexes for the kinetic resolution of terminal epoxides via carbon dioxide coupling (Figure 4) [27].…”

Section: Other Metal Salen Complexesmentioning

confidence: 99%

Synthesis of Chiral Cyclic Carbonates via Kinetic Resolution of Racemic Epoxides and Carbon Dioxide

Castro‐Osma

North

2016

Symmetry

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“…Lu and co-workers [26] first described the preparation of optically pure cyclic carbonates from racemic epoxides by a catalytic kinetic resolution process involving several chiral (salen)CoX complexes and quaternary ammonium halides. And the reaction of racemic propylene oxide with 0.55-0.60 equiv of CO 2 was catalyzed by 0.1 mol % of (salen)Co III (O 2 CCCl 3 ) complex 2b and 0.1 mol % of n-Bu 4 NBr under solvent-free conditions.…”

Section: (Salen)cr For the Coupling Of Co 2 And Epoxidesmentioning

confidence: 99%

Catalytic Processes for Chemical Conversion of Carbon Dioxide into Cyclic Carbonates and Polycarbonates

Miao¹,

Wang²,

2008

TOOCJ

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Chemical fixation of CO 2 has received much attention because CO 2 is the most inexpensive and renewable carbon resource from the viewpoint of green chemistry and atom economy. The kinetic and thermodynamic stability of CO 2 molecule presents significant challenges in designing efficient chemical transformations based on this potential feedstock. Currently, cyclic carbonates and polycarbonates are both valuable products, and the coupling of CO 2 and epoxides is one of the most promising and eco-friendly methods for chemical conversion of CO 2 into cyclic carbonates and/or polycarbonates. In this review, we will mainly discuss the synthesis of polycarbonates or cyclic carbonates catalyzed by metalsalen complexes through adjusting the architecture of the ligands and optimizing reaction conditions, such as temperature, pressure, co-catalysts, epoxide concentration. Furthermore, the recent progress for the synthesis of cyclic carbonates via the coupling reactions of epoxides and CO 2 mediated by both homogeneous and heterogeneous catalysts is particularly reviewed.

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Asymmetric Catalysis with CO₂: Direct Synthesis of Optically Active Propylene Carbonate from Racemic Epoxides

Abstract: This communication describes a convenient route to optically active propylene carbonate by a catalytic kinetic resolution process resulting from the coupling reaction of CO2 and racemic epoxides using simple chiral SalenCo(III)/quaternary ammonium halide catalyst systems.

Cited by 346 publications

References 29 publications

Recent Advances in the Catalytic Preparation of Cyclic Organic Carbonates

Recent Advances in the Catalytic Preparation of Cyclic Organic Carbonates

Synthesis of Chiral Cyclic Carbonates via Kinetic Resolution of Racemic Epoxides and Carbon Dioxide

Catalytic Processes for Chemical Conversion of Carbon Dioxide into Cyclic Carbonates and Polycarbonates

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Asymmetric Catalysis with CO2: Direct Synthesis of Optically Active Propylene Carbonate from Racemic Epoxides

Abstract: This communication describes a convenient route to optically active propylene carbonate by a catalytic kinetic resolution process resulting from the coupling reaction of CO2 and racemic epoxides using simple chiral SalenCo(III)/quaternary ammonium halide catalyst systems.

Cited by 346 publications

References 29 publications

Recent Advances in the Catalytic Preparation of Cyclic Organic Carbonates

Recent Advances in the Catalytic Preparation of Cyclic Organic Carbonates

Synthesis of Chiral Cyclic Carbonates via Kinetic Resolution of Racemic Epoxides and Carbon Dioxide

Catalytic Processes for Chemical Conversion of Carbon Dioxide into Cyclic Carbonates and Polycarbonates

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Asymmetric Catalysis with CO₂: Direct Synthesis of Optically Active Propylene Carbonate from Racemic Epoxides