Copper catalyzed enantioselective [4＋2] annulations of D-A cyclobutanes and aldehydes have been developed. In the presence of a side arm modified chiral bisoxazoline （SaBOX） ligand, the [4＋2] annulations proceeded...Copper catalyzed enantioselective [4＋2] annulations of D-A cyclobutanes and aldehydes have been developed. In the presence of a side arm modified chiral bisoxazoline （SaBOX） ligand, the [4＋2] annulations proceeded smoothly with a broad substrate scope. 22 examples were studied, leading to the corresponding products with various functional groups in 41%-99% yields with 〉99/1 dr and 90%-96% ee. The resulting product with two ester groups was mono-reduced, giving the corresponding product in excellent diastereoselectivity without loss of the enantiopurity.展开更多
An efficient,chromium-catalyzed highly enantioselective preparation of protected 1,3-diols has been achieved.In the presence of a chiral chromium catalyst using the carbazole-based bisoxazoline as the chiral ligand,a ...An efficient,chromium-catalyzed highly enantioselective preparation of protected 1,3-diols has been achieved.In the presence of a chiral chromium catalyst using the carbazole-based bisoxazoline as the chiral ligand,a variety of optically pure 1,3-diols were synthesized in 34%-87%yields with up to 98%ee.The benzyl as well as silyl ethers were suitable substitutions for the hydroxyl group.Meanwhile,aromatic,aliphatic and α,β-unsaturated aldehydes are well tolerated under the mild reaction conditions.展开更多
Enantioselective chlorination of b-keto esters and amides catalyzed by squaramide-linked bisoxazoline ligand–Cu（OAc）2complexes was investigated. The corresponding chlorinated products were obtained in excellent yie...Enantioselective chlorination of b-keto esters and amides catalyzed by squaramide-linked bisoxazoline ligand–Cu（OAc）2complexes was investigated. The corresponding chlorinated products were obtained in excellent yields with moderate enantioselectivities. The effect of solvent, temperature, Lewis acid, and ligand structure on the reaction is discussed. This was the first investigation of catalytic asymmetric achlorination of b-keto amides. This study has highlighted that a simple chiral squaramide–oxazoline with cheap Cu（OAc）2 H2 O complexes can catalyze this chlorination.展开更多
Four novel bisoxazoline ligands 8a-d were synthesized from （S）-amino alcohols and could be formed effective catalysts （up to 77% ee for endo isomer） with Cu（OTf）2 for enantioselective Diels-Alder addition. The f...Four novel bisoxazoline ligands 8a-d were synthesized from （S）-amino alcohols and could be formed effective catalysts （up to 77% ee for endo isomer） with Cu（OTf）2 for enantioselective Diels-Alder addition. The facility of the reaction was dependent on the nature of the substituent R in the bisoxazoline ligand.展开更多
A new type of chiral bisoxazoline ligands 1 based on spiro[4,4]-1,6-nonadiene backbone was easily prepared in six steps from racemic spiro[4,4]-nonane-1,6-dione,with the Pd-catalyzed coupling of the enol triflates wit...A new type of chiral bisoxazoline ligands 1 based on spiro[4,4]-1,6-nonadiene backbone was easily prepared in six steps from racemic spiro[4,4]-nonane-1,6-dione,with the Pd-catalyzed coupling of the enol triflates with CO and amino alcohols as the key steps for the construction of the oxazoline moiety. The structure of the ligand (R,S,S)-1b was unambiguously established by X-ray crystallographic analysis. The chiral Cu(II) complex generated in situ from the combination of spiro bisoxazoline ligand (S,S,S)-1c and Cu(OTf)2 was effective in the catalysis of asymmetric chlorination of the β-ketoester,methyl 1-oxo-2,3-dihydro-1H-indene-2-carboxylate,affording the corresponding chlorinated derivative in 99% yield with 17% ee.展开更多
A highly efficient asymmetric cyclopropanation of trisubstituted olefins with methyl diazoacetate has been developed in terms of an elaborate modified chiral bisoxazoline/copper complex as a catalyst. A broad scope of...A highly efficient asymmetric cyclopropanation of trisubstituted olefins with methyl diazoacetate has been developed in terms of an elaborate modified chiral bisoxazoline/copper complex as a catalyst. A broad scope of substrates is compatible with this catalyst system, including various trisubstituted olefins bearing different aryl-, fused aryl-and alkyl-substituents, providing an easy access to optically active 1,1-dimethyl cyclopropanes in good yields with excellent diastereo-and enantio-selectivity.展开更多
A novel class of chiral spiro-fused bisoxazoline ligands possessing a deep chiral pocket was prepared.The developed ligands have been employed in the nickel-catalyzed highly enantioselective Michael-type Friedel-Craft...A novel class of chiral spiro-fused bisoxazoline ligands possessing a deep chiral pocket was prepared.The developed ligands have been employed in the nickel-catalyzed highly enantioselective Michael-type Friedel-Crafts reaction, affording the products bearing a trifluoromethylated all-carbon quaternary stereocenter with moderate to excellent yields(up to 99%) and good to excellent enantioselectivies(up to> 99.9% ee). Moreover, a proposed model of chiral pocket revealed that the attack of indole from the Re-face of β-CF_(3)-β-disubstituted nitroalkene was favorable.展开更多
A copper-catalyzed highly stereoselective cyclopropanation of 1,2-disubstituted olefins with α-nitrodiazo acetates has been developed, giving the desired products in up to 97 % yields, up to 〉99/1 dr and up to 98 % ...A copper-catalyzed highly stereoselective cyclopropanation of 1,2-disubstituted olefins with α-nitrodiazo acetates has been developed, giving the desired products in up to 97 % yields, up to 〉99/1 dr and up to 98 % ee, which provides an efficient access to the synthesis of optical active cyclopropane α-amino acids and unnatural α-amino acid derivatives.展开更多
基金We thank for the financial support from the National Natural Science Foundation of China （Nos. 21421091 and 21432011）, the National Basic Research Program of China （973 Program） （2015CB856600）, the Natural Science Foundation of Shanghai （17ZR1436900）, the Strategic Priority Research Program of the Chinese Academy of Sciences （Grant No. XDB20000000） and the Youth Innovation Promotion Association CAS （2017301）. We thank Dr. Xue-Bing Leng for X-ray crystal analysis
文摘Copper catalyzed enantioselective [4＋2] annulations of D-A cyclobutanes and aldehydes have been developed. In the presence of a side arm modified chiral bisoxazoline （SaBOX） ligand, the [4＋2] annulations proceeded smoothly with a broad substrate scope. 22 examples were studied, leading to the corresponding products with various functional groups in 41%-99% yields with 〉99/1 dr and 90%-96% ee. The resulting product with two ester groups was mono-reduced, giving the corresponding product in excellent diastereoselectivity without loss of the enantiopurity.
基金NSFC(Nos.21421091,XDB20000000)the "Thousand Plan" Youth program for financial support
文摘An efficient,chromium-catalyzed highly enantioselective preparation of protected 1,3-diols has been achieved.In the presence of a chiral chromium catalyst using the carbazole-based bisoxazoline as the chiral ligand,a variety of optically pure 1,3-diols were synthesized in 34%-87%yields with up to 98%ee.The benzyl as well as silyl ethers were suitable substitutions for the hydroxyl group.Meanwhile,aromatic,aliphatic and α,β-unsaturated aldehydes are well tolerated under the mild reaction conditions.
基金financial support from the National Natural Science Foundation of China(Nos.21072010 and 21272024)
文摘Enantioselective chlorination of b-keto esters and amides catalyzed by squaramide-linked bisoxazoline ligand–Cu（OAc）2complexes was investigated. The corresponding chlorinated products were obtained in excellent yields with moderate enantioselectivities. The effect of solvent, temperature, Lewis acid, and ligand structure on the reaction is discussed. This was the first investigation of catalytic asymmetric achlorination of b-keto amides. This study has highlighted that a simple chiral squaramide–oxazoline with cheap Cu（OAc）2 H2 O complexes can catalyze this chlorination.
基金Finacial support by the National Natural Science Foundation of China(No.2047211)the Science Foundation of China Agricultural University(No.2005058)is gratefully acknowledged.
文摘Four novel bisoxazoline ligands 8a-d were synthesized from （S）-amino alcohols and could be formed effective catalysts （up to 77% ee for endo isomer） with Cu（OTf）2 for enantioselective Diels-Alder addition. The facility of the reaction was dependent on the nature of the substituent R in the bisoxazoline ligand.
基金supported by the National Natural Science Foundation of China (20821002 and 20972176)the Chinese Academy of Sciences, the National Basic Research Program of China (2010CB833300),the Science and Technology Commission of Shanghai Municipality,and Merck Research Laboratories
文摘A new type of chiral bisoxazoline ligands 1 based on spiro[4,4]-1,6-nonadiene backbone was easily prepared in six steps from racemic spiro[4,4]-nonane-1,6-dione,with the Pd-catalyzed coupling of the enol triflates with CO and amino alcohols as the key steps for the construction of the oxazoline moiety. The structure of the ligand (R,S,S)-1b was unambiguously established by X-ray crystallographic analysis. The chiral Cu(II) complex generated in situ from the combination of spiro bisoxazoline ligand (S,S,S)-1c and Cu(OTf)2 was effective in the catalysis of asymmetric chlorination of the β-ketoester,methyl 1-oxo-2,3-dihydro-1H-indene-2-carboxylate,affording the corresponding chlorinated derivative in 99% yield with 17% ee.
基金supported by the National Natural Science Foundation of China(21432011,21772224)Key Research Program of Frontier Sciences of Chinese Academy of Sciences(QYZDY-SSWSLH016)+2 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB20000000)the Youth Innovation Promotion Association CAS(2017301)the National Basic Research Program of China(2015CB856600)
文摘A highly efficient asymmetric cyclopropanation of trisubstituted olefins with methyl diazoacetate has been developed in terms of an elaborate modified chiral bisoxazoline/copper complex as a catalyst. A broad scope of substrates is compatible with this catalyst system, including various trisubstituted olefins bearing different aryl-, fused aryl-and alkyl-substituents, providing an easy access to optically active 1,1-dimethyl cyclopropanes in good yields with excellent diastereo-and enantio-selectivity.
基金support from the National Natural Science Foundation of China(No.21871067)the Natural Science Foundation of Guangdong Province(Nos.2018A030313038 and 2021A1515010190)+3 种基金the Shenzhen Fundamental Research Projects(No.JCYJ20180306171838187)the Harbin Institute of Technology(Shenzhen)(Talent Development Starting Fund from Shenzhen Government)the Open Project Program of State Key Laboratory of Elemento-Organic Chemistry(No.202009)the Guangdong Provincial Key Laboratory of Catalysis(No.2020B121201002)。
文摘A novel class of chiral spiro-fused bisoxazoline ligands possessing a deep chiral pocket was prepared.The developed ligands have been employed in the nickel-catalyzed highly enantioselective Michael-type Friedel-Crafts reaction, affording the products bearing a trifluoromethylated all-carbon quaternary stereocenter with moderate to excellent yields(up to 99%) and good to excellent enantioselectivies(up to> 99.9% ee). Moreover, a proposed model of chiral pocket revealed that the attack of indole from the Re-face of β-CF_(3)-β-disubstituted nitroalkene was favorable.
基金supported by the National Natural Science Foundation of China(21421091,21432011 and21272250)the Chinese Academy of Sciences
文摘A copper-catalyzed highly stereoselective cyclopropanation of 1,2-disubstituted olefins with α-nitrodiazo acetates has been developed, giving the desired products in up to 97 % yields, up to 〉99/1 dr and up to 98 % ee, which provides an efficient access to the synthesis of optical active cyclopropane α-amino acids and unnatural α-amino acid derivatives.
