Construction of the Cyclophane Core of the Hirsutellones via a RCM Strategy

Huang, Mingzheng; Song, Li; Liu, Bo

doi:10.1021/ol100692x

Cited by 35 publications

(15 citation statements)

References 49 publications

(22 reference statements)

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“…Despite the fact that cyclophanes have been extensively synthesized and evaluated because of their unique physical and chemical properties, examples of the isolation and total synthesis of cyclophane-containing natural products are rare and challenging. This has attracted the interest of synthetic chemists in search of new and efficient strategies for syntheses with a reduced number of steps [45,46]. …”

Section: Introductionmentioning

confidence: 99%

Quinone and Hydroquinone Metabolites from the Ascidians of the Genus Aplidium

et al. 2014

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Ascidians of the genus Aplidium are recognized as an important source of chemical diversity and bioactive natural products. Among the compounds produced by this genus are non-nitrogenous metabolites, mainly prenylated quinones and hydroquinones. This review discusses the isolation, structural elucidation, and biological activities of quinones, hydroquinones, rossinones, longithorones, longithorols, floresolides, scabellones, conicaquinones, aplidinones, thiaplidiaquinones, and conithiaquinones. A compilation of the 13C-NMR spectral data of these compounds is also presented.

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Section: Introductionmentioning

confidence: 99%

Quinone and Hydroquinone Metabolites from the Ascidians of the Genus Aplidium

et al. 2014

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“…The clear message here is that the direct synthesis of [ n ]paracyclophanes can be a challenging, but solvable problem. A similar reaction was used in synthetic work on the hirsutellones 133. In this case, RCM of 225 led to the formation of a 1:1 mixture of two atropisomeric 10paracyclophanes 226 and 227 in 69 % combined yield (Scheme ).…”

Section: Ring‐closing Metathesismentioning

confidence: 95%

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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“…Structurally, it has a highly strained 13-membered cyclic ring and a tricyclic decahydrofluorene skeleton [110]. There are several strategies toward the total synthesis of this challenging macrocycle [111,112,113,114,115,116]. Recently, Uchiro and coworkers accomplished the total synthesis of hirsutellone B by using copper-catalyzed Ullmann-type reaction as a critical cyclic step (Scheme 14) [117].…”

Section: Chemical Methodologies For the Construction Of Macrocyclesmentioning

confidence: 99%

Macrocyclic Drugs and Synthetic Methodologies toward Macrocycles

2013

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Macrocyclic scaffolds are commonly found in bioactive natural products and pharmaceutical molecules. So far, a large number of macrocyclic natural products have been isolated and synthesized. The construction of macrocycles is generally considered as a crucial and challenging step in the synthesis of macrocyclic natural products. Over the last several decades, numerous efforts have been undertaken toward the synthesis of complex naturally occurring macrocycles and great progresses have been made to advance the field of total synthesis. The commonly used synthetic methodologies toward macrocyclization include macrolactonization, macrolactamization, transition metal-catalyzed cross coupling, ring-closing metathesis, and click reaction, among others. Selected recent examples of macrocyclic synthesis of natural products and druglike macrocycles with significant biological relevance are highlighted in each class. The primary goal of this review is to summarize currently used macrocyclic drugs, highlight the therapeutic potential of this underexplored drug class and outline the general synthetic methodologies for the synthesis of macrocycles.

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Construction of the Cyclophane Core of the Hirsutellones via a RCM Strategy

Abstract: Construction of the highly strained [10]-paracyclophane core of the hirsutellones has been completed via an effective RCM strategy.

Cited by 35 publications

References 49 publications

Quinone and Hydroquinone Metabolites from the Ascidians of the Genus Aplidium

Quinone and Hydroquinone Metabolites from the Ascidians of the Genus Aplidium

Olefination Reactions in the Synthesis of Cyclophanes

Macrocyclic Drugs and Synthetic Methodologies toward Macrocycles

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