Synthese von [2]‐Catenanen aus [2]‐Rotaxanen

Schill, Gottfried; Schweickert, Norbert; Fritz, Hans; Vetter, Walter

doi:10.1002/cber.19881210522

Cited by 26 publications

(35 citation statements)

References 21 publications

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“…A catenane synthesis from the Schill laboratory which sticks out from the remainder of his work method‐wise and target‐wise is detailed in Scheme , Scheme , and Scheme . Method‐wise this study is noteworthy because it describes the synthesis of a catenane from a rotaxane (the first conversion of that kind was published 12 years earlier by Zilkha et al).…”

Section: Catenanes From Freiburg and A Rotaxane → Catenane Conversionmentioning

confidence: 99%

“…The top half of Scheme shows Schill's access to the key building blocks of his catenane‐from‐rotaxane endeavor: They were the ω‐bromo‐C 13 ‐alkyne 55 (usage: Scheme ), the ω‐(trityloxy)‐C 11 ‐bromide 56 (usage: Scheme ), and the C 28 ‐cycloalkane 65 (usage: Scheme ). The ω‐bromo‐C 13 ‐alkyne 55 was derived from the ω‐bromo‐C 11 ‐alcohol 28 by adding it to dihydropyran, introducing lithium acetylide, cleaving the THP ether, and substituting OH by Br . The ω‐(trityloxy)‐C 11 ‐bromide 56 stemmed from the ω‐bromo‐C 11 ‐alcohol 28 and trityl chloride .…”

Section: Catenanes From Freiburg and A Rotaxane → Catenane Conversionmentioning

confidence: 99%

“…The ω‐bromo‐C 13 ‐alkyne 55 was derived from the ω‐bromo‐C 11 ‐alcohol 28 by adding it to dihydropyran, introducing lithium acetylide, cleaving the THP ether, and substituting OH by Br . The ω‐(trityloxy)‐C 11 ‐bromide 56 stemmed from the ω‐bromo‐C 11 ‐alcohol 28 and trityl chloride . The synthesis of the C 28 ‐cycloalkane 65 began with an acylation of two equivalents of morpholinocyclohexene ( 57 ) by dodecanedioic dichloride ( 58 ) .…”

Section: Catenanes From Freiburg and A Rotaxane → Catenane Conversionmentioning

confidence: 99%

“…Its keto groups were removed by a Wolff‐Kishner reduction giving the C 24 ‐dicarboxylic acid 61 . Both ends of this compound were subjected to the sequence CO 2 H → CO 2 Me → CH 2 OH ( 62 ) → CH 2 Br ( 63 ) → CH 2 C≡CH . An intramolecular Glaser coupling ensued, establishing the 28‐membered cycloalkadiyne 64 in 77 % yield .…”

Section: Catenanes From Freiburg and A Rotaxane → Catenane Conversionmentioning

confidence: 99%

“…The article at hand recalls the 1958 to 1988/1993 achievements in Freiburg regarding catenanes , rotaxanes , and molecular knots . At their time they were highly unusual compounds.…”

Section: Introductionmentioning

confidence: 99%

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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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Section: Catenanes From Freiburg and A Rotaxane → Catenane Conversionmentioning

confidence: 99%

Section: Catenanes From Freiburg and A Rotaxane → Catenane Conversionmentioning

confidence: 99%

Section: Catenanes From Freiburg and A Rotaxane → Catenane Conversionmentioning

confidence: 99%

Section: Catenanes From Freiburg and A Rotaxane → Catenane Conversionmentioning

confidence: 99%

“…The article at hand recalls the 1958 to 1988/1993 achievements in Freiburg regarding catenanes , rotaxanes , and molecular knots . At their time they were highly unusual compounds.…”

Section: Introductionmentioning

confidence: 99%

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