Optically Active Polycarbonates:  Asymmetric Alternating Copolymerization of Cyclohexene Oxide and Carbon Dioxide

Nozaki, Kyoko; Nakano, Koji; Hiyama, Tamejiro

doi:10.1021/ja992433b

Cited by 226 publications

(143 citation statements)

References 22 publications

Supporting

Mentioning

136

Contrasting

Unclassified

Order By: Relevance

“…Very recently, iron À corrole complexes were synthesized by Nozaki and co-workers 24 to copolymerize epoxides with CO 2 , providing the first example of iron-catalysed PO (propylene oxide)/CO 2 and GPE (glycidyl phenyl ether)/CO 2 copolymerization. The same group also demonstrated the stereoselective alternating copolymerization of cyclohexene oxide and CO 2 with dimeric zinc complexes for the first time 25 . Besides, improved catalysts are still desirable to better control the properties of the resulting materials 26 .…”

Section: Box 1 | Coordination Modes Of Co 2 With Transition Metalsmentioning

confidence: 96%

Using carbon dioxide as a building block in organic synthesis

et al. 2015

View full text Add to dashboard Cite

Carbon dioxide exits in the atmosphere and is produced by the combustion of fossil fuels, the fermentation of sugars and the respiration of all living organisms. An active goal in organic synthesis is to take this carbon-trapped in a waste product-and re-use it to build useful chemicals. Recent advances in organometallic chemistry and catalysis provide effective means for the chemical transformation of CO 2 and its incorporation into synthetic organic molecules under mild conditions. Such a use of carbon dioxide as a renewable one-carbon (C1) building block in organic synthesis could contribute to a more sustainable use of resources.A more sensible resource management is the prerequisite for the sustainable development of future generations. However, when dealing with the feedstock of the chemical industry, the level of sustainability is still far from satisfactory. Until now, the vast majority of carbon resources are based on crude oil, natural gas and coal. In addition to biomass, CO 2 offers the possibility to create a renewable carbon economy. Since pre-industrial times, the amount of CO 2 has steadily increased and nowadays CO 2 is a component of greenhouse gases, which are primarily responsible for the rise in atmospheric temperature and probably abnormal changes in the global climate. This increase in CO 2 concentration is largely due to the combustion of fossil fuels, which are required to meet the world's energy demand 1 . Obviously, there is an urgent need to control CO 2 emissions and develop efficient carbon capture systems. Although the extensive use of carbon dioxide for chemical production cannot solve this problem alone, CO 2 is a useful one-carbon (C1) building block in organic synthesis due to its abundance, availability, nontoxicity and recyclability. As a result, valorization of CO 2 is currently receiving considerable and ever increasing attention by the scientific community 2-4 . However, activation and utilization of CO 2 is still problematic due to the fact that it is the most oxidized form of carbon, which is also thermodynamically stable and/or kinetically inert in certain desired transformations. Consequently, most of the known studies used highly reactive substrates and/or severe reaction conditions to activate CO 2 , limiting the application of such methods. In particular, the catalytic coupling of CO 2 with energy-rich substrates, such as epoxides and aziridines, to generate polycarbonates/polycarbamates and/or cyclic carbonates/carbamates has drawn significant attention over the past decades. To create C-C bonds with CO 2 , the use of carbon nucleophiles is specifically limited to strong nucleophilic organolithiums and Grignard reagents, as well as phenolates.

show abstract

Section: Box 1 | Coordination Modes Of Co 2 With Transition Metalsmentioning

confidence: 96%

Using carbon dioxide as a building block in organic synthesis

et al. 2015

View full text Add to dashboard Cite

show abstract

“…Nozaki and coworkers 72,73 have succeeded with meso-desymmetrization in the alternating copolymerization of carbon dioxide and cyclohexene oxide with the complex obtained by the equimolar reaction between diethylzinc and an optically active (S)-diphenyl(pyrrolidin-2-yl)methanol (14). At 60°C under 30 atm in 24 h, the alternating copolymer was obtained in a high yield (M n ϭ 13,000; M w /M n ϭ 3.6).…”

Section: Asymmetric Copolymerizationmentioning

confidence: 99%

Copolymerization of carbon dioxide and epoxide

Sugimoto

Inoue

2004

J. Polym. Sci. A Polym. Chem.

360

142

View full text Add to dashboard Cite

An erratum has been published for this article in J Polym Sci Part A: Polym Chem (2005) 43(4) 916.The alternating copolymerization of carbon dioxide and epoxide to produce polycarbonate has attracted the attention of many chemists because it is one of the most promising methodologies for the utilization of carbon dioxide as a safe, clean, and abundant raw material in synthetic chemistry. Recent development of catalysts for alternating copolymerization is based on the rational design of metal complexes, particularly complexes of transition metals with well‐defined structures. In this article, the history and recent successful examples of the alternating copolymerization of carbon dioxide and epoxide are described. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5561–5573, 2004

show abstract

“…The first attempt of asymmetric copolymerization of CO 2 with cyclohexene oxide (CHO) was disclosed by Nozaki et al using a 1:1 Et 2 Zn/(S)-a,a-diphenyl(pyrrolidin-2-yl)methanol mixture as catalyst, producing the corresponding polycarbonates with moderate enantioselectivity. [2] Soon thereafter, the Coates research group reported the use of chiral hybrid imineoxazoline zinc-based catalysts for this reaction, which showed similar enantioselectivity but higher activity and controlled molecular weight. [3] Further mechanistic studies suggested that a dimeric zinc complex might be the active species.…”

mentioning

confidence: 99%