Medium-Sized Cyclophanes, 63.<sup>1</sup> Synthesis and Structure of [2.2]Metacyclophane-1,2-Diol and Conversion Into [2.2]Metacyclophane-1,2-Dione by Swern Oxidation

Yamato, Takehiko; Hironaka, Toru; Saisyo, Tatsunori; Manabe, Tomoki; Okuyama, Ken-ichiro

doi:10.3184/030823403103173183

Cited by 11 publications

(1 citation statement)

References 23 publications

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“…Some general comments can be made about the performance of the McMurry reactions. First, the reaction failed for the syntheses of the smallest, most strained systems ( n =2, 88 d ,54 88 h ,55 88 l 56) with one notable exception, [2.2]metacyclophan‐1‐ene 88 q ,58 which was obtained in 4.3 % yield. This product stands out not only because it is a highly strained [2.2]metacyclophane, but also because it is a [2.2]metacyclophane with internal substituents, which add to the strain!…”

Section: The Mcmurry 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: The Mcmurry and Related Reactionsmentioning

confidence: 99%

Olefination Reactions in the Synthesis of Cyclophanes

Bodwell

Nandaluru

2012

Israel Journal of Chemistry

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The McMurry Coupling and Related Reactions

Takeda

Tsubouchi

2013

Organic Reactions

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The McMurry coupling reaction has been recognized as one of the most efficient methods for the synthesis of alkenes from carbonyl compounds. This reaction can be applied to the preparation of various alkenes that are otherwise difficult to prepare. For example, sterically congested tetrasubstituted alkenes as well as medium to large membered rings involving natural products may be accessed via this process. This coupling utilizes various low‐valent titanium reagents generated by the reduction of titanium (III or IV) chloride with K, Zn, LiAlH 4 , C 8 K, amongst others. Furthermore, a variety of low‐valent metal species other than titanium, including aluminum, zirconium, niobium, molybdenum, indium, tungsten, and samarium, have also been found to promote the reductive coupling of carbonyl compounds. The scope and limitations of these reagent systems are reviewed in this chapter, together with the stereochemistry and reaction mechanism. This reaction is categorized into four coupling modes: i) homocoupling giving symmetrical alkenes, ii) mixed coupling giving unsymmetrical alkenes, iii) intramolecular coupling giving cycloalkenes, and iv) tandem coupling giving cyclic polyenes. Characteristics of these reaction modes are described briefly. A selection of synthetic applications are reviewed, including examples of the preparation of sterically congested and strained alkenes, medium to large‐ring compounds, biologically active targets, as well as substrates applicable in material science. Experimental conditions used for this versatile process are summarized to assist the choice of suitable conditions.

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Moffatt‐Swern Oxidation

2010

Comprehensive Organic Name Reactions and Reagents

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The oxidation of primary and secondary alcohols to carbonyl compounds (aldehydes and ketones) from dimethyl sulfoxide (DMSO) in combination with oxalyl chloride and triethylamine under anhydrous conditions is generally known as the Moffatt–Swern oxidation. The combination of oxalyl chloride, DMSO, and triethylamine is called the Swern‐Moffatt reagent. It has been reported that this reaction involves the formation of an ylide through an alkoxydimethylsulfonium ion. Because this reaction is very mild and selective, it has been widely used in organic synthesis. This reaction also has some disadvantages. This reaction has wide application in the preparation of ketones and aldehydes.

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Medium-Sized Cyclophanes, 63.¹ Synthesis and Structure of [2.2]Metacyclophane-1,2-Diol and Conversion Into [2.2]Metacyclophane-1,2-Dione by Swern Oxidation

Abstract: McMurry cyclisation of 1,2-bis(5- t-butyl-2-methyl-3-formylphenyl)ethane 2 afforded anti-[2.2]metacyclophan-1-ene 3 and anti-[2.2]metacyclophane-1,2-diols 4, which were converted into the corresponding 1,2-dione 6 by Swern oxidation.

Cited by 11 publications

References 23 publications

Olefination Reactions in the Synthesis of Cyclophanes

Olefination Reactions in the Synthesis of Cyclophanes

The McMurry Coupling and Related Reactions

Moffatt‐Swern Oxidation

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Medium-Sized Cyclophanes, 63.1 Synthesis and Structure of [2.2]Metacyclophane-1,2-Diol and Conversion Into [2.2]Metacyclophane-1,2-Dione by Swern Oxidation

Abstract: McMurry cyclisation of 1,2-bis(5- t-butyl-2-methyl-3-formylphenyl)ethane 2 afforded anti-[2.2]metacyclophan-1-ene 3 and anti-[2.2]metacyclophane-1,2-diols 4, which were converted into the corresponding 1,2-dione 6 by Swern oxidation.

Cited by 11 publications

References 23 publications

Olefination Reactions in the Synthesis of Cyclophanes

Olefination Reactions in the Synthesis of Cyclophanes

The McMurry Coupling and Related Reactions

Moffatt‐Swern Oxidation

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Medium-Sized Cyclophanes, 63.¹ Synthesis and Structure of [2.2]Metacyclophane-1,2-Diol and Conversion Into [2.2]Metacyclophane-1,2-Dione by Swern Oxidation