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排序方式: 共有187条查询结果,搜索用时 15 毫秒
171.
172.
Vincent Terrasson Dr. Renata Marcia de Figueiredo Dr. Jean Marc Campagne Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(26):7875-7880
An enantioselective cyclopropanation of α‐substituted α,β‐unsaturated aldehydes with bromomalonate has been successfully developed through a domino Michael/α‐alkylation strategy. The method allows the efficient formation of cyclopropanes bearing a quaternary carbon stereocenter at the α‐position of the aldehydes by using iminium/enamine catalysis and gives a nice extension on the organocatalytic cyclopropanation of bromomalonate and α,β‐unsaturated aldehydes previously reported by other groups. Very good yields (up to 81 %) and enantioselectivities (up to 97 % ee) have been obtained. The optically active cyclopropane derivatives are of high synthetic interest as useful targets for further elaboration into more complex structures. 相似文献
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174.
Prashant A. Waske 《Tetrahedron》2005,61(43):10321-10330
Various ring-fused cyclopropyl silyl ethers with an benzylic, olefinic or acetylenic side chain have been synthesized. Upon oxidative photoinduced electron transfer (PET) the cyclopropane ring opens and forms a reactive β-keto radical, which undergoes intramolecular cyclization. In some cases we observed only formation of ring opened non-cyclized products. With olefinic side chain 5-exo-trig mode of cyclization rather than 6-endo-trig mode of cyclization takes place whereas in case of acetylenic side chain we observed 6-endo cyclization. 相似文献
175.
de Meijere A Becker H Stolle A Kozhushkov SI Bes MT Salaün J Noltemeyer M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(8):2471-2482
The trimethylsilyl-protected enynes 9a-c and 14a,b with alkynyl substituents on the three-membered ring or on the double bond of a methylenecyclopropane or a bicyclopropylidene moiety were prepared in two steps from the alcohols 6a-c and 12a,b, respectively, by conversion to the iodides and their coupling with lithium (trimethylsilyl)acetylide (8) in 38-73% overall yields. The bicyclopropylidene derivative 9d was synthesized in 49% yield directly from bicyclopropylidene (3) by lithiation followed by coupling with (5-iodopent-1-ynyl)trimethylsilane (11). Enynes 9b-d were protiodesilylated by treatment with K2CO3 in methanol to give the corresponding unprotected enynes 10b-d in 53, 74 and 94% yield, respectively. Enynes 17a-c with a carbonyl group adjacent to the acetylenic moiety were synthesized from oxo derivatives 15a-c by Wittig olefination followed by coupling with 8 in 47, 18 and 12% overall yield, respectively. Pauson-Khand reactions of the methylenecyclopropane derivatives with a substituent on the ring (9a,b and 10a) as well as on the double bond (14a,b and their in situ prepared protiodesilylated analogues) proceeded smoothly by stirring of the corresponding enyne with [Co2(CO)8] in dichloromethane at ambient temperature followed by treatment of the formed complexes with trimethylamine N-oxide under an oxygen atmosphere at -78 degrees C to give tricyclic or spirocyclopropanated bicyclic enones 18a,b, 19a, 20a,b, 21a,b in good yields. Alkynylbicyclopropylidene derivatives 9c,d and 10c,d formed the corresponding cobalt complexes at -78 to -20 degrees C. Treatment of the latter with N-methylmorpholine N-oxide under an argon atmosphere at -20 degrees C gave the spirocyclopropanated tricyclic enones 18c, 19c and 18d in 31-45% yields. The structure of 19c was proved by X-ray crystal structure analysis. The cyclization of enynones 17a-c in MeCN at 80 degrees C gave the spirocyclopropanated bicyclic diketones 22a-c in 38-65% yields. Intramolecular PKRs of the enynes 25a,d with a chiral auxiliary adjacent to the triple bond gave the corresponding products 26a,d in 70 and 79% yield, respectively, as 5:1 and 8:1 mixtures of diastereomers, respectively. Addition of lithium dimethylcuprate or higher order cuprates to the double bond of the former furnished bridgehead-substituted bicyclo[3.3.0]octanones 27a-c in 57-86% yields. Protiodesilylation of 27a followed by acetal cleavage gave the enantiomerically pure spirocyclopropanated bicyclo[3.3.0]octanedione (1R,5R)- 29a with [alpha]D(20)=-148 (c=1.0 in CHCl3) in 55% overall yield. 相似文献
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179.
Heiko Rinderhagen 《Tetrahedron》2006,62(27):6589-6593
Siloxy cyclopropanes undergo ring opening and fragmentation of formal silyl cations under formation of β-keto radicals. These reactive intermediates can be used in inter- and intramolecular addition reactions leading to complex ring systems if more than one unsaturated side chain is present in the starting material. Beside some synthetic examples mainly the mechanism will be discussed focusing on the structure of the primarily formed radical cations, the regioselectivity of cyclopropane cleavage (endo vs exo ring opening), leaving of the silyl group, and termination by H-transfer. 相似文献
180.
Julietta Yedoyan Nikolai Wurzer Urszula Klimczak Thomas Ertl Oliver Reiser 《Angewandte Chemie (International ed. in English)》2019,58(11):3594-3598
A palladium‐catalyzed coupling between aryl halides and monocyclopropanated pyrroles or furans has been developed, leading to valuable six‐membered N‐ and O‐heterocycles. As the key step, a selective cleavage of the non‐activated endocyclic C?C bond of the 2‐heterobicyclo‐[3.1.0]hexane framework is achieved. The developed method offers access to highly functionalized piperidines, pyridines, and pyrans that are challenging to access by traditional methods. 相似文献