共查询到20条相似文献,搜索用时 13 毫秒
1.
2.
3.
4.
《Tetrahedron letters》1986,27(21):2397-2400
Pd catalyzed reaction of perfluoroalkyl and polyfluoroalkyl iodides with tertiary amines gave enamines(1) which on acid hydrolysis afforded enaminones(2), or aldehydes(3). 相似文献
5.
Evidence for the existence of two mechanistic pathways for the reaction of secondary perfluoroalkyl iodides with zinc has been obtained. At high concentration of secondary iodides, a bimolecular homolytic type reaction of the iodide on the zinc surface to yield dimers appears to be preferred. When the reaction is carried out under dilute conditions, an ionic type mechanism appears to predominate. This paper also shows that the substrate itself can influence the reaction route. 相似文献
6.
Catalytic amounts of zinc, as low as 10 mol %, in the presence of trifluoroacetic acid (TFA) initiate the radical addition of perfluoroalkyl iodides to terminal alkynes with high regio- and stereoselectivities. Palladium-mediated cross-coupling of these (E)-perfluoroalkyl vinyl iodides allows for a facile synthesis of potentially useful fluoroorganic intermediates. 相似文献
7.
Fluoroalkyl iodide RfI [RF=(CF2)nCl, n=2, 4, 6; CF3(CF2)n, n=1, 3; H(CF2)4] reacted with alkyne (CH≡CC4H9; CH≡CSiMe3; CH≡CC6H5) in the presence of catalytic amounts of tetrakis (triphenylphosphine) palladium (0) to give a mixture of E and Z-fluoroalkylated adduct. The reaction could not be catalyzed by dichloro-bis(triphenylphosphine)palladium (II) and fluoroalkyl complex of palladium (II). 2-Nitro-2-nitrosopropane partly suppressed the reaction. It is believed that the reaction proceeds through a free radical intermediate rather than fluoroalkyl complex of palladium (II). 相似文献
8.
9.
Dependent on the selection of the light sources employed, the photoinduced iodoperfluoroalkylation of a variety of unsaturated compounds takes place efficiently via a radical mechanism. Upon irradiation with a xenon lamp through Pyrex (hnu >300 nm), terminal alkenes (R-CH=CH2) and alkynes (R-C triple bond CH) undergo iodoperfluoroalkylation with perfluoroalkyl iodides (RF-I) regioselectively, providing R-CH(I)-CH2-RF and R-C(I)=CH-RF, respectively. In the case of terminal allenes (R-CH=C=CH2), the photoinduced iodoperfluoroalkylation occurs selectively at the terminal double bond, giving the corresponding beta-perfluoroalkylated vinylic iodides (R-CH=C(I)-CH2-RF) in good yields. The photoinitiated reaction of vinylcyclopropanes (c-C3H5-C(R)=CH2) with RF-I proceeds via the rearrangement of cyclopropylcarbinyl radical intermediates to the homoallylic radical intermediates, and the corresponding 1,5-iodoperfluoroalkylated products (I-(CH2)2CH=C(R)-CH2-RF) are obtained in high yields. Isocyanides (R-NC), as C-N unsaturated compounds, also undergo the xenon-lamp-irradiated iodoperfluoroalkylation to provide the corresponding 1,1-adducts (R-N=C(I)-RF) in good yields. Furthermore, the present photoinitiation procedure can be applied to the iodotrifluoromethylation of unsaturated compounds, when the xenon-lamp-irradiated reactions are conducted under the refluxing conditions of excess CF3-I. 相似文献
10.
合成了仲碘代全氟烷衍生物CF~3CFI(CF~2)~2O(CF~2)~2SO~2F(3),CF~3(CFI(CF~2)~2O(CF~2)~2SO~3Na(4),CF~3CFI(CF~2)~nCl(7an=2,7bn=4)及CF~2(CF~2)~3OCFICF~3(8),研究了它们与连二亚硫酸钠的反应,并用烯烃作为自由基截捕剂加入反应体系中,得到了1:1仲碘代全氟烷与各类烯烃的加成物. 相似文献
11.
Reaction of perfluoroalkyl iodides with a series of alkynes under sulfinatodehalogenation condition gave a mixture of E/Z adducts very readily in high yield, thus constituted a mild, convenient and effective new method for the addition of perfluoroalkyl iodides to alkynes. Under the same condition, in the presence of 1-hexyne perfluoroalkyl bromide and 1,1,1-trichlorotrifluoroethane reacted only to give sulfinates as the major products. A radical mechanism was proposed for the addition reaction. 相似文献
12.
[reaction--see text] Aryl iodides anchored to Merrifield resin via the linkages between a carboxyl, hydroxyl, or hydroxymethyl group and the benzylic chloride moiety in the resin reacted efficiently with 1,2-allenic carboxylic acids under the catalysis of Pd(0) to afford polymer-supported butenolides. Polysubstituted butenolides can be easily cleaved from the resins by Lewis acid-catalyzed processes in good yields and purities. 相似文献
13.
全氟碘代烷R~FI[R~F=CF~3(CF~2)~5(1a);H(CF~2)~4(1b);H(CF~2)~8(1c);Cl(CF~2)~6(1d);Cl(CF~2)~8(1e)Cl(CF~2)~8(1f);;NaO~3S(CF~2)~20(CF~2)~2(1g);NaO~3S(CF~2)~2O(CF~2)~4(1h)]及α,ω-二碘化物I(CF~2)~nI[n=4(1i);n=6(1j)]与Ce^4^+-亚硫酸氢钠于70℃左右、pH3~4的溶液中反应,形成相应的全氟烷基亚磺酸盐,产率70~85%。全氟氯代烷和全氟溴代烷在同样条件下未能发生反应。 相似文献
14.
Perfluoroalkyl iodides serve as excellent mediators for the radical cyclization of dienes, diynes, and enynes upon irradiation with near-UV light, providing the corresponding iodoperfluoroalkylated cyclic compounds in moderate to good yields. 相似文献
15.
Several derivatives of secondary perfluoroalkyl iodides such as CF3CFI(CF2)2O(CF2)3SO2F (3), CF3CFI(CF2),O(CF2)2SO3Na (4), CF3CFI(CF3)n Cl (n=2, 7a; n=4, 7b) and CF3(CF2)2-OCFICF3 (8) were synthesized using known methods, their reaction with sodium dithionite was studied and various olefins were added into the reaction system as radical traps to yield the 1:1 radical adducts. 相似文献
16.
Perfluoroalkyl iodides reacted with conjugated dienes in aqueous acetonitrile solution in the presence of sodium dithionite at room temperature to give dimerization products, whereas, perfluoroalkanesulfonyl bromides reacted with conjugated dienes to form 1,4-adducts under actinic irradiation. 相似文献
17.
The atom-efficient cross-coupling of triarylbismuths with aryl iodides or aryl triflates using catalytic Pd(OAc)2/PPh3 and K3PO4 as base in DMF at 90 °C to afford the corresponding functionalized biaryls in high yields is reported. 相似文献
18.
Organotin dihalides R2SnX2 (X Cl, Br, I) and their adducts with bidentate donor ligands have been prepared in high yield by the direct electrochemical reaction of metallic tin with alkyl or aryl halides in organic media at room temperature. Dimethyltin diiodide can be converted to tetramethyltin by reaction with methyl iodide at a cadmium anode. Electrochemical halide abstraction has been used to prepare R6Sn2 (R Me, Ph) from the corresponding R3Sn halide. The mechanism of these reactions is discussed. 相似文献
19.
Yasushi Obora Angelo S. Baleta Makoto Tokunaga Yasushi Tsuji 《Journal of organometallic chemistry》2002,660(2):173-177
In the presence of a catalytic amount (5 mol%) of a platinum complex, tributyltin cyanide (1) reacts with dimethyl- (2a) or diethyl acetylenedicarboxylate (2b) to afford cyanostannylation adducts (3a, b) in excellent yields. The reaction proceeds highly selectively affording only a (Z)-isomer. The compounds 3a, b are novel products which possess synthetically useful cyano, alkenylstannyl and alkoxycarbonyl functionalities in the same molecule. Two alkoxycarbonyl functionalities may be indispensable on each alkyne carbon to accomplish the cyanostannylation reaction. Reaction with terminal alkynes gave the stannylated product (6). 相似文献
20.
Thermal and redox-induced telomerizations of vinylidene fluoride (VDF) with linear (n-C4F9I) or branched (i-C3F7I) perfluoroalkyl iodides have been performed. In both cases, thermal telomerizations led to telomeric-type distributions of the first five (from linear telogen) or the first three (from branched telogen) adducts produced, with better yields at higher temperatures. The redox-initiated telomerization was more selective since it led to the first two adducts only. For both reactions, mono- and di-adducts were isolated and characterized by 1H and 19F NMR spectroscopy. Interestingly, both the diadducts were composed of two isomers (i.e. the expected telomer and RFCH2CF2CF2CH2I). Two mechanisms are proposed and it is assumed that the products may be obtained either by chain propagation or by stepwise telomerization. In addition, attack of the electrophilic radical on the nucleophilic side of VDF is discussed. 相似文献