Synthesis of [3.3](1,1’) and [5.5](1,1’)FERROCENOPHANE Derivatives

Kasahara, Akira; Izumi, Taeko; Shimizu, I.

doi:10.1246/cl.1979.1317

Cited by 9 publications

(4 citation statements)

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“…The aldol condensation has been exploited infrequently in the synthesis of cyclophanes. A thirty year old example is the synthesis of three ferrocenophanes using base‐catalyzed aldol condensation 158. Condensation of 1,1′‐ferrocenedicarboxaldehyde ( 99 ) with acetone afforded [5.5]ferrocenophane 283 (32 %) (Scheme ).…”

Section: Aldol Condensations and Related Reactionsmentioning

confidence: 99%

Olefination Reactions in the Synthesis of Cyclophanes

Bodwell

Nandaluru

2012

Israel Journal of Chemistry

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A survey of olefination reactions that have been used in the synthesis of cyclophanes is presented. This covers the Ramberg-Bäcklund reaction, the Wittig and related reactions, the McMurry and related reactions, ring-closing metathesis (alkenes, alkynes and ene-ynes), aldol condensations and Siegrist reactions, as well as miscellaneous reactions. The McMurry reaction and ring-closing metathesis have enjoyed the greatest popularity in recent years, but they are typically used for complementary purposes. In virtually all cases, the McMurry reaction is used to install a twocarbon (1,2-ethenylene) bridge, whereas ring-closing metathesis is used to construct bridges that are at least fourmembered, but usually considerably longer. Some wellknown olefinations have seen little or no use in the field of cyclophane chemistry.The Ramberg-Bäcklund reaction [9] is the final step in a two-to three-step thioether-to-alkene conversion. As such, it appears to be well-suited for the synthesis of alkene-containing cyclophanes. Even though it applies to pre-existing cyclophanes, it warrants attention in the context of this review because both bonds of the newly formed alkene are generated during the reaction. Within the broader scope of organic synthesis, the Ramberg-Bäcklund reaction has been exploited frequently to introduce a double bond into large rings, [10] small rings [11] and more exotic ring systems such as cyclic enediynes. [12] However, it has not performed well in the synthesis of cyclophanes.The first cyclophanes to be synthesized using the Ramberg-Bäcklund reaction were the isomeric biphenylophanes (Z,Z)-7 and (E,E)-7 (Scheme 3). [13] As expected from mechanistic considerations, [14] they were formed stereospecifically in good yield (both 65 %) from the diastereomeric sulfones meso-6 and (AE)-6, respectively. Interestingly, the report of these very good results came shortly after Boekelheide wrote that "the Ramberg-Bäcklund reaction is unsatisfactory when applied to 2,11-dithia-[3.3]cyclophanes". [15] Prior to Boekelheides comment on the Ramberg-Bäcklund reaction, Martel reported that a Ramberg-Prof. Graham Bodwell obtained his B.Sc. and M.Sc. from the University of Victoria, Canada, working with Prof. Reginald Mitchell on cyclophanes. He then moved to Braunschweig, Germany, where he joined the group of Prof. Dr. Henning Hopf as a "Doktorand". Cyclophanes were also the focus of his doctoral research. He then took a break from cyclophanes and worked in the field of asymmetric synthesis as a post-doctoral fellow with Prof. Steve Davies at Oxford University. He then accepted a faculty position at Memorial University, where he now holds the rank of Professor. Cyclophanes have always been one of his core research interests.Penchal Reddy Nandaluru obtained his B.Sc. and M.Sc. from Sri Venkateswara University, India, and then worked as a chemist with AVRA Laboratories in India before joining the group of Prof. Graham Bodwell at Memorial University in St. John's, NL, Canada. The main theme of his doctoral research is the appli...

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Section: Aldol Condensations and Related Reactionsmentioning

confidence: 99%

Olefination Reactions in the Synthesis of Cyclophanes

Bodwell

Nandaluru

2012

Israel Journal of Chemistry

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“…20 a,b-Unsaturated hydroxamic acids undergo intramolecular cyclization with Li 2 PdCl 4 in anhydrous MeCN (Scheme 15). 21…”

Section: Scheme 14mentioning

confidence: 99%

β-Oxidation of α,β-Unsaturated Carbonyl Compounds

Sommer¹

2004

Synthesis

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The replacement of a b-hydrogen on an a,b-unsaturated carbonyl system with a non-hydrogen, non-carbon atom amounts to either a net two electron oxidation or an isohypsic substitution at the b-carbon. The resulting compounds are the functional equivalents of b-dicarbonyl derivatives. Although many methods have been developed to effect this transformation, they lack generality and the process remains an underutilized one in organic synthesis.

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“…While [m.n]ferrocenophanes with m, n = 0, 1, 2 have been investigated to some extent, derivatives with m, n > 2 have much less been explored. For example, [4.4]ferrocenophane has been reported by Lüttringhaus et al .,, and few derivatives of [3.3]‐ and [5.5]ferrocenophane have been prepared by Kasahara et al ,. Diarsane 10 is one of the very rare [m.n]ferrocenophanes with heteroatoms in the bridges.…”

Section: Introductionmentioning

confidence: 99%

“…[20,21] While [m.n]ferrocenophanes with m, n = 0, 1, 2 have been investigated to some extent, derivatives with m, n > 2 have much less been explored. For example, [4.4]ferrocenophane has been reported by Lüttringhaus et al, [22,23] and few derivatives of [3.3]-and [5.5]ferrocenophane have been prepared by Kasahara et al [24,25] Diarsane 10 is one of the very rare [m.n] ferrocenophanes with heteroatoms in the bridges. The compound has been obtained by Kauffmann et al by treatment of the dianionic ligand system with iron(II) chloride in 2% yield as the side product in addition to the respective mononuclear arsa [5]ferrocenophane, no further reactions have been mentioned.…”

Section: Introductionmentioning

confidence: 99%

1,16‐Di‐tert‐butyl‐1,16‐diphospha[5.5]ferrocenophane: Synthesis, Reactions and Mössbauer Spectroscopy

et al. 2018

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1,16‐Di‐tert‐butyl‐1,16‐diphospha[5.5]ferrocenophane was prepared in 76% yield by deprotonation of 1,1’‐di(2‐tert‐butylphosphanylethyl)ferrocene followed by treatment with 1,1’‐di(2‐bromoethyl)ferrocene. The ferrocenophane exists as a mixture of syn and anti diastereomers, which were separated by repeated precipitation of one of them. Reaction with borane afforded the respective borane adducts in 47% yield. Methylation with iodomethane gave the respective diphosphonium salt in quantitative yield. Oxidation with 1.0 or 5.0 equivalents of silver hexafloroantimonate gave a green and a blue material, respectively, presumably the mono and the diferrcenium salts. 1,16‐Di‐tert‐butyl‐1,16‐diphospha[5.5]ferrocenophane and its oxidation products were subjected to a temperature‐dependent Mössbauer effect (ME) study to elucidate their dynamical and paramagnetic relaxation characteristics. The ME data are consistent with the absence of spin averaging for the two distinct Fe sites in the monooxidation product over the temperature range 91

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Synthesis of [3.3](1,1’) and [5.5](1,1’)FERROCENOPHANE Derivatives

Cited by 9 publications

References 1 publication

Olefination Reactions in the Synthesis of Cyclophanes

Olefination Reactions in the Synthesis of Cyclophanes

β-Oxidation of α,β-Unsaturated Carbonyl Compounds

1,16‐Di‐tert‐butyl‐1,16‐diphospha[5.5]ferrocenophane: Synthesis, Reactions and Mössbauer Spectroscopy

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