Default Latest Most Read Please wait a minute... REVIEWS Recent Advance of Transition-Metal-Catalyzed Tandem Carboxylation Reaction of Unsaturated Hydrocarbons with Organometallic Reagents and CO2 Yaping Yi, Wei Hang, Chanjuan Xi Chinese Journal of Organic Chemistry 2021, 41 (1): 80-93. DOI: 10.6023/cjoc202007013 Published: 09 September 2020 Abstract (984) HTML (53) PDF (809KB)(1319) Knowledge map Carbon dioxide (CO 2), as a one-carbon synthon, has many advantages such as abundant, non-toxic, clean and so on. So the reactions using CO 2 as a one-carbon synthon have been widely concerned in organic chemistry. Transition-metal- catalyzed reaction of unsaturated hydrocarbons with CO 2 to produce carboxylic acid is one of the most commonly-used method to convert CO 2, and organometallic reagents can be added to the reaction as reducing agent. This kind of reaction can be realized by the strategy of tandem reaction. In the reaction, the unsaturated hydrocarbons react with transition-metal catalysts and organometallic reagents to generate new organometallic reagents in situ first, and then complete carboxylation with CO 2. Common organometallic reagents such as organozinc reagents, Grignard reagents, and organoaluminum reagents can all achieve this kind of carboxylation reaction. In this review, reactions are divided according to the type of unsaturated hydrocarbons, and each type can also be divided into hydrocarboxylation and carbocarboxylation. This review would introduce reaction according to this classification. Fig. & Tab. | Reference | Related Articles | Metrics HIGHLIGHTS Rh(I)-Catalyzed Regioselective Arylcarboxylation of Acrylamides with Arylboronic Acids and CO2 Wei Hang, Chanjuan Xi Chinese Journal of Organic Chemistry 2021, 41 (1): 425-427. DOI: 10.6023/cjoc202100004 Abstract (408) HTML (12) PDF (396KB)(421) Knowledge map Fig. & Tab. | Reference | Related Articles | Metrics Recent Progress in the Carboxylation/Cyclization Reactions Using Carbon Dioxide as the C1 Source Zhou Cong, Li Miao, Yu Jintao, Sun Song, Cheng Jiang Chinese Journal of Organic Chemistry 2020, 40 (8): 2221-2231. DOI: 10.6023/cjoc202003039 Published: 15 May 2020 Abstract (1804) PDF (694KB)(1410) Knowledge map Carbon dioxide is a readily available, low-cost, abundant, non-toxic C1 source, which can potentially serve as an ideal building block in synthetic chemistry. Recently, much progress, expecially multi-component reactions (MCRs) has been achieved in construction of carbonyl-containing heterocycles through annulation by using carbon dioxide as carbonyl/carboxyl source. Herein, the advances on the annulation reaction of atmospheric CO2 with N-, and O-nucleophiles for the constructioin of various carbonyl-containing heterocycles, including benzoxazin, cyclic carbamates, lactams, oxazolidine-2,4-diones are reviewed. In addition, the carboxylation of C-nucleophiles with CO2 toward carboxylic acids is also summarized. Reference | Related Articles | Metrics Recent Advances of CO2 Fixation via Asymmetric Catalysis for the Direct Synthesis of Optically Active Small Molecules Guo Xiao, Wang Yazhou, Chen Jie, Li Gongqiang, Xia Ji-Bao Chinese Journal of Organic Chemistry 2020, 40 (8): 2208-2220. DOI: 10.6023/cjoc202002032 Published: 15 May 2020 Abstract (1445) PDF (818KB)(1358) Knowledge map Industrial processes of fixing carbon dioxide (CO2) lag far behind the carbon emission generated by human activity. Since CO2 is an abundant, non-toxic, and cost-effective one carbon source, it is highly desirable to develop methodologies on converting CO2 into valuable products for sustainable purpose. Based on the mechanistic insight of CO2 activation by transition-metal catalyst and organocatalyst, a variety of efficient asymmetric CO2 chemical fixation processes have been developed in recent years. This review discusses the advances of enantioselective synthesis of small molecules by asymmetric catalytic reactions with CO2. The interaction between catalyst, CO2 and substrate has been elaborated aiming to inspire the design of new catalytic systems for asymmetric CO2 transformation. Reference | Related Articles | Metrics Advance and Prospective on CO2 Activation and Transformation Strategy Chen Kaihong, Li Hongru, He Liangnian Chinese Journal of Organic Chemistry 2020, 40 (8): 2195-2207. DOI: 10.6023/cjoc202004030 Published: 01 June 2020 Abstract (1340) PDF (711KB)(2213) Knowledge map Climate change and depletion of fossil fuels have drawn considerable attention. Considering carbon dioxide is both the dominant greenhouse gas and renewable C1 source, CO2 valorization into valuable chemicals is considered to reconcile the environment benefit and sustainable chemistry development. Unfortunately, the thermodynamic stability and kinetic inertness of CO2 make its chemical transformation challenging. As a consequence, developing highly efficient catalytic systems and synthetic protocols is crucial for CO2 conversion. In recent years, He's group made great progress on strategy design and catalyst development for CO2 conversion. A series novel CO2 conversion strategies are proposed, including CO2 capture and in-situ transformation, hierarchical reductive functionalization of CO2, designing thermodynamically favorable reactions by multi-component cascade reaction and photo-promoted CO2 transformation. Concurrently, the corresponding highly efficient catalytic systems were also developed based on the reaction mechanism and thus CO2 transformation was successfully performed under mild conditions. It is hoped that this review can arouse broad concern on CO2 transformation and spur its further development. Reference | Related Articles | Metrics Catalytic Asymmetric Construction of All-Carbon Quaternary Stereocenters via Coupling of CO2 with 1,3-Dienes Cheng Lei, Xie Jianhua Chinese Journal of Organic Chemistry 2020, 40 (1): 247-248. DOI: 10.6023/cjoc202000005 Abstract (664) PDF (377KB)(749) Knowledge map Reference | Related Articles | Metrics Synthesis of o-Halothiobenzamide Derivatives from the Selective Thiolysis Reaction of o-Halobenzonitrile Mediated by CO2 Sang Guozhi, Feng Xuetong, Chen Juan, Li Shanshan, Li Zhuona, Li Xiao, Han Limin, Hong Hailong, Zhu Ning Chinese Journal of Organic Chemistry 2019, 39 (12): 3542-3549. DOI: 10.6023/cjoc201904063 Published: 01 August 2019 Abstract (373) PDF (602KB)(497) Knowledge map A method for the selective synthesis of o-halothiobenzamide by thiolysis reaction of o-halobenzonitrile with NaHS under the action of CO2 was explored. CO2/H2O/NaHS was used as a buffer system to provide a suitable pH environment, which would make HS- attack the nitrile-based carbon selectively to produce the corresponding o-halothiobenzamide. Moreover, the buffer system also provided the additionally required hydrogen atom for the thiolysis reaction of o-haloben-zonitrile with NaHS. Further studies have found that the CO2/Na2S·9H2O buffer system could also efficiently promote the thiolysis reaction of o-halobenzonitrile to form the corresponding o-halothiobenzamide. This synthetic method could be used to prepare different substituted o-halobenzonitriles, which is a simple, efficient and high atom-economic reaction. Reference | Supporting Info. | Related Articles | Metrics ARTICLES Carbonyl Cobalt-Catalyzed Cyclotrimerization of Terminal Alkynes in Supercritical Carbon Dioxide Wang, Yaqi, Yin, Qiang, Guo, Dun, Han, Limin, Sun, Qi, Hong, Hailong, Suo, Quanling, Suo. Quanling Chinese Journal of Organic Chemistry 2019, 39 (10): 2898-2905. DOI: 10.6023/cjoc201904021 Published: 28 May 2019 Abstract (689) HTML (17) PDF (561KB)(556) Knowledge map Atom-efficient [2+2+2] cycloaddition reaction of alkynes in green solvent supercritical carbon dioxide (ScCO2) is an environmentally friendly reaction process that conforms to the principles of green chemistry. Cyclotrimerization of terminal alkynes catalyzed by Co2(CO)8 in pure ScCO2 has been studied to obtain 1,2,4-trisubstituted benzene derivatives with excellent selectivity. The reaction conditions for the cyclotrimerization were optimized, such as concentration of catalyst, CO2 pressure, reaction temperature and time. The solubility and phase behavior of the reaction materials and catalysts in ScCO2 medium were discussed, and the mechanism of Co2(CO)8 catalyzed cyclotrimerization of terminal alkynes was assumed. The reaction substrate was extended from C≡C (alkyne) to C≡N (nitrile), and the alkyne-nitrile cycloaddition reaction in ScCO2 was preliminary explored. Our optimized catalytic system for the cyclotrimerization of terminal alkynes exhibited wide substrate scope and high product selectivity, in which no organic co-solvent or additives were added. It provided a green synthetic method for 1,2,4-trisubstituted benzenes. Fig. & Tab. | Reference | Related Articles | Metrics ARTICLES Pyridine Bridged Organocatalyst for the Synthesis of 3-Aryl-2-oxazolidinones from Carbon Dioxide, Terminal Epoxide, and Aryl Amine Liu, Quanyao, Shi, Lei, Liu, Ning Chinese Journal of Organic Chemistry 2019, 39 (10): 2882-2891. DOI: 10.6023/cjoc201903030 Published: 03 June 2019 Abstract (673) HTML (13) PDF (1028KB)(509) Knowledge map A series of carboxyl group or hydroxyl group functionalized organocatalysts were synthesized and applied in three component reaction of carbon dioxide with epoxide, and aryl amines for the synthesis of 3-aryl-2-oxazolidinones. The method allows the reaction to proceed smoothly in the mild reaction conditions, together with excellent substrates scope of epoxides and aryl amines. The control experiments suggest that the cyclic carbonates are formed by the coupling of epoxides with carbon dioxide, which further react with the amino alcohol generated from epoxides and aryl amines, finally resulting in the desired products. Fig. & Tab. | Reference | Related Articles | Metrics