Unusual Fluoroalkenylation of Porphyrins: A Highly Stereoselective Synthesis of 10,20‐Diaryl‐5‐[(<i>E</i>)‐fluoroalkenyl]‐15‐(fluoroalkyl)porphyrins

Jin, Li‐Mei; Chen, Liang; Xiao, Ji‐Chang; Guo, Can‐Cheng; Chen, Qing‐Yun

doi:10.1002/ejoc.200600130

Cited by 4 publications

(3 citation statements)

References 26 publications

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“…IR spectra were recorded on a Perkin-Elmer Spectrum 100 FT-IR spectrometer. Starting Materials: Formylporphyrins 1a, [29] 1b; [30] bromoporphyrins 4a, [31] 4j, [32] 4l; [31] dipyrromethane [15] , 5,15-disubstituted porphyrins: 8a, [33] 8b, [14b] 8c, [34] 8d, [14b] 8e, [35] 8f, [36] 10a, [37] 5,10,15-triphenylporphyrin 9a and the nickel(II) complex 11a, [39] and 5,15-bis(4-methylphenyl)-10-phenylporphyrin (9b) [40] were prepared using standard methodologies and had analytical data consistent with that in the literature. General Procedure A.…”

Section: Methodsmentioning

confidence: 99%

Synthesis and Reactivity of Allenylporphyrins

2013

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Several different methods have been utilized in an effort to allow for the effective the effective synthesis of a new class of porphyrins, bearing the synthetically intriguing propadienyl (or allenyl) functional group. Of these, successive HWE couplings proved impossible, but Pd-catalyzed cross couplings enabled quick and easy synthetic access to allenylporphyrins. Suzuki-Miyaura cross coupling conditions of bromoporphyrins with allenylboronic acid pinacol ester were optimized and represent the first successful use of this boronic acid in a Suzuki-type coupling. While this routine proved successful for the synthesis of porphyrins possessing aromatic substituents a more robust method involving Sonogashira coupling of a bromoporphyrin with N,Ndiisopropylprop-2-yn-1-amine followed by Pd catalyzed rearrangement was developed to give allenylporphyrins in high yields. The applicable metalation states of the porphyrin core were also investigated in both routes with mixed results. The utility of the addition of the allenyl functional group was then probed using both directly linked allenylporphyrins and those bearing a phenyl "spacer".____________ [a]

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Section: Methodsmentioning

confidence: 99%

Synthesis and Reactivity of Allenylporphyrins

2013

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“…If acidic workup was used, trifluoroethylene 169 was not formed and derivative 168b was isolated exclusively. The mechanism of trifluoroethylene 169 formation is depicted in Scheme . It includes reduction of monofluoroalkylated porphyrin 168c to form carbanion intermediate 170 .…”

Section: Chemical Properties Of Polyfluorinated Ethanesmentioning

confidence: 99%

Polyfluorinated Ethanes as Versatile Fluorinated C2-Building Blocks for Organic Synthesis

2015

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“…of Na 2 S 2 O 4 in DMSO/CH 2 Cl 2 /H 2 O (20 : 20 : 1) at 50 1C for 1 h, after which the reaction mixture was acidified with aqueous HCl solution (37%, w/w) and allowed to react for a further 1 h, to give 258 and 259 in moderate yield (Scheme 74). 90 The use of 2% water (v/v) as a co-solvent was necessary, otherwise only trace amounts of the products were detected, even after 24 h. Interestingly, treating the same reaction mixture of 253a 0 and CF 3 (CF2) 5 I with triethylamine (TEA) rather than acidifying with aqueous HCl solution gave the (E)-isomer 260c in 50% yield (Scheme 74). Other bases, such as NaHCO 3 , K 2 CO 3 and pyridine, could also achieve the same results and provided 260 in high yield.…”

Section: Synthesis Of Fluoroalkylated Porphyrins Under Modified Sulfi...mentioning

confidence: 99%

Progress in fluoroalkylation of organic compounds via sulfinatodehalogenation initiation system

et al. 2012

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The sulfinatodehalogenation reaction represents one of the most important methodologies to incorporate fluorine into organic molecules. Using inexpensive sulfur-containing reactants such as Na(2)S(2)O(4) under mild conditions, per- and polyfluoroalkyl halides (R(F)X, X = Br, I, CCl(3)) can be transformed smoothly into the corresponding sulfinate salts. This method is also used for the perfluoroalkylation of alkenes, dienes, alkynes and aromatics. Notably, after 1998, the sulfinatodehalogenation of perfluoroalkyl chlorides (R(F)Cl) has been realized by using dimethylsulfoxide (DMSO) as a solvent instead of CH(3)CN/H(2)O in the Na(2)S(2)O(4)/NaHCO(3) initiation system. Perfluoroalkyl chlorides, ethyl chlorofluoroacetates and chlorodifluoroacetates, and even nonfluorinated compounds, such as ethyl chloro- or dichloroacetates and chloroform, were either converted into the corresponding sulfinate salts or alkylated alkenes, alkynes and aromatics (including porphyrins). The sulfinatodehalogenation reaction has remarkable advantages. With the increasing demands to utilize the unique properties of fluorine and fluorinated functional groups in medicinal, agricultural and material sciences, we believe that there will continue to be useful developments in sulfinatodehalogenation chemistry and it will be applied more widely in the future.

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Unusual Fluoroalkenylation of Porphyrins: A Highly Stereoselective Synthesis of 10,20‐Diaryl‐5‐[(E)‐fluoroalkenyl]‐15‐(fluoroalkyl)porphyrins

Cited by 4 publications

References 26 publications

Synthesis and Reactivity of Allenylporphyrins

Synthesis and Reactivity of Allenylporphyrins

Polyfluorinated Ethanes as Versatile Fluorinated C2-Building Blocks for Organic Synthesis

Progress in fluoroalkylation of organic compounds via sulfinatodehalogenation initiation system

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