[3]‐Catenane durch gezielte Synthese

Schill, Gottfried; Zürcher, Clemens

doi:10.1002/cber.19771100604

Cited by 35 publications

(4 citation statements)

References 36 publications

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“…During this time, there was considerable discussion of chemical topology instigated by Frisch and Wasserman, 92 and of topological stereochemistry popularised by Walba 93 at the University of Colorado in Boulder, while Schill 94 (and Lu¨tteringhaus) in Freiburg painstakingly introduced the first directed synthesis of catenanes, rotaxanes and knots onto the scene with the use of covalent templation. In this much more highly planned approach, multiple-step (often 420) syntheses were employed in the preparation of [2]catenanes, 95,96 [2]rotaxanes 96 and [3]catenanes 97,98 as well as of molecular knots. 99 Many of the synthetic strategies relied at the end of the day on the ability to hydrolyse cyclic acetals and to cleave aryl-nitrogen bonds in the later stages of the synthesis.…”

Section: Reflectionsmentioning

confidence: 99%

The chemistry of the mechanical bond

2009

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The use of templation in the synthesis of unnatural products where two or more components are mechanically interlocked has not only raised the efficiency of their production to near quantitative levels in some instances, but the molecular recognition that aids and abets the templation is also part and parcel of the molecules after they have been prepared, purified and presented for investigation. The fact that the molecular recognition 'lives on' in mechanically interlocked molecules, following their templated formation, makes them prime candidates for applications that straddle the scientific and technical worlds from devices that could spawn new information technologies to integrated systems that could have fundamental applications in the health-care industries. The challenge to make more and more sophisticated compounds is predicated upon our fundamental understanding of the nature of the mechanical bond and how this associated knowledge base can be employed to do complex systems chemistry in very different environments where emergent phenomena become the order of the day (critical review, 104 references).

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Section: Reflectionsmentioning

confidence: 99%

The chemistry of the mechanical bond

2009

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“…Schill produced his blueprint for the use of covalent templation in the synthesis of ''Catenanes, Rotaxanes and Knots'' in the form of a monograph published 7 in 1971. During almost a quarter of a century, Schill demonstrated the application of covalent-directed templated synthesis to the production of [2]catenanes, 8,9 [2]rotaxanes 9 and [3]catenanes 10,11 as well as molecular knots. 12 There were two issues that, most unfortunately, diminished the value of Schill's epic contributions to the chemistry of MIMs.…”

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confidence: 99%

The master of chemical topology

Stoddart

2009

Chem. Soc. Rev.

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“…3) The route of Scheme to the mixture of constitutionally isomeric [3]catenanes C 2v ‐ and C s ‐ 97 , shares some features with the route to the [2]catenane of Scheme and the route to the [3]catenanes of Scheme and Scheme . A resorcinol ( 90 ) and the long‐chain ω,ω′‐dichloroketone 30 are condensed to form a ketal ( 91 ).…”

Section: Catenanes From Freiburg and A Rotaxane → Catenane Conversionmentioning

confidence: 96%

Pioneering Work on Catenanes, Rotaxanes, and a Knotane in the University of Freiburg 1958–1988

Brückner

2019

Eur J Org Chem

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Research at the University of Freiburg is summarized which aimed at realizing catenanes, rotaxanes, and a molecular knot from 61–62 until 41 years ago. Taking a fresh view at ansa‐compounds – distinct from those in which he had been interested for other reasons before – Arthur Lüttringhaus began to tackle syntheses of catenanes in 1957. The first isolation of a pure catenane (37) succeeded in 1964 jointly with Gottfried Schill. Most of the progress made in the sequel was due to Schill alone or achieved under his direction; in addition, a few follow‐up studies were published without Schill or Lüttringhaus being their authors. The major feats of these endeavors were the syntheses of the following molecules: (1) the first catenanes (38 – de‐acetyl‐41, 74) without a ring in any constituent (this feature makes them unique till today; the catenane 74 holds the additional record of being the only all‐hydrocarbon catenane till now); the first [3]catenanes at all (obtained as a mixture of constitutional isomers C2v‐97 and C2h‐97); the first [3]catenanes exhibiting topological isomerism (89, iso‐89, and neo‐iso‐89); the rotaxanes 70 [which had the design peculiarity of being convertible into a catenane (74)], 113 (Schill's #1‐rotaxane), and 115; the pre‐knotane rac‐dia‐iso‐123 [provided it was obtained and not (only) its topological isomer dia‐iso‐123]. – For due perspectives, pertinent studies of third parties are included, too: 1) Wasserman's reports on the isolation of the catenane 8 are analyzed in great detail; the conclusion is that the identity of 8 was never established. 2) Schill's oscillating rotaxane 70 from 1988, which is subject to a reversible and non‐degenerate ring migration (→ iso‐70), is supplemented by Stoddart's much faster oscillating rotaxane 71 from 1991, which undergoes a reversible and degenerate ring migration (→ 71 instead of → iso‐71) and was dubbed “molecular shuttle”. 3) The first [3]catenanes from the groups of Schill (97; 1969), Sauvage (98 and 99; 1985), and Stoddart (100–102; 1991) are juxtaposed. 4) The Harrisons' synthesis of the rotaxane 106 by a most noteworthy solid‐phase approach (1967) is recalled in the context of Schill's synthesis of the rotaxane 113 (1967 or 1969). 5) Attempts at threading α‐cyclodextrin by long‐chain 1,ω‐dithiols (→ 130) and ring‐closing the latter oxidatively for obtaining catenated disulfides failed in Lüttringhaus' 1957/1958 studies; in contrast, Stoddart's threading permethyl‐β‐cyclodextrin (133) by the long‐chain 1,ω‐diamine 132 and ring‐closing the latter by a double condensation with terephthaloyl dichloride was successful by providing 3 % of the catenated bislactame 134 in 1993. The concluding section characterizes the synthetic strategies towards catenanes and rotaxanes developed in Freiburg as “template‐based”. This differs from the Nobel Prize Committee's assessment.

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[3]‐Catenane durch gezielte Synthese

Cited by 35 publications

References 36 publications

The chemistry of the mechanical bond

The chemistry of the mechanical bond

The master of chemical topology

Pioneering Work on Catenanes, Rotaxanes, and a Knotane in the University of Freiburg 1958–1988

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