Catenanes statistical approaches

As stated above, simple catenanes were first obtained by a statistical approach. However, the successful syntheses of more complicated topological molecules would not have been possible without an enforcement of spatial orientation of reaction substrates called preorganization, introduced in Section 2.3. The latter effect can be achieved by... 

I was intrigued. Mulling over the problem later that evening, and considering the need both to form and to detect catenanes, a statistical approach seemed attractive. Synthesis of a C30 ring from a linear precursor in the presence of an inert C20 cyclic compound should enable threading of some of the smaller rings before cyclization. A C50 product would indicate the presence of an interlocked system. 

There are two distinct approaches to catenane synthesis the statistical approach, and approaches relying on self-assembly, so-called directed synthesis . The statistical approach relies on the small chance that macrocyclisation may occur while a linear precursor is threaded through a macrocyclic component. Because this is a rather unlikely eventuality, it naturally results in low yields of interlinked product and is chiefly of historical interest. It was this kind of statistical approach that resulted in the first synthesis of a [2] catenane by Wasserman in 1960 (10.64), from cyclisation of the long-chain diester 10.65 while threaded through the annulus of a deuterated C34 cycloalkane 10.66 (Scheme 10.11), 57 Although the overall yield of the catenation reaction was less than 1 %, the existence of the catenane was firmly established. The relatively polar [2] catenane product, along with other polar macrocyclisation reaction products and... 

Scheme 10.11 The first catenane synthesis via the statistical approach.57...

Early attempts at the synthesis of catenanes were based on the so-called statistical approach. For example, according to this approach, a molecular thread X Y, functionalized on both ends, may enter into a macrocycle of adequate size subsequent cyclization of X-Y leads to two interlocked rings. Since the probability that cyclization occurs while X-Y is threaded through the macrocycle is very small, only poor yields can be expected. 

Frisch, H.L. and Wasserman, E. (1961) Chemical topology, J. Am. Chem. Soc. 83, 3789-3794. Schill, G. (1971) Catenanes, rotaxanes and knots. Academic Press, New York. Walba, D.M. (1985) Topological stereochemistry. Tetrahedron 41, 3161-3212. Dietrich-Buchecker, C.O. and Sauvage, J.P. (1987) Interlocking of molecular threads From the statistical approach to the templated synthesis of catenands, Chem. Rev. 87, 795-810. Philp, D. and Stoddart, J.F. (1991) Self-assembly in organic synthesis, Synlett 445-458. 

SCHEME 10.1 Synthesis of the first reported catenane 1 which relied on a statistical approach. ... 

After the very early achievements due to the real pioneers of chemical topology who forty years ago first acceeded to that intriguing molecule that is a catenane (by statistical threading approach Wasserman, 1960 or by a directed approach Liittringhaus and Schill, 1964), this peculiar field of research concerned with molecules whose prime feature rests without doubt on beauty and non trivial spacial arrangement, has in the beginning of the 80 s literaly exploded with the apparition of various templated approaches. 

It was not only for the basic scientific knowledge but also for the new challenges in the synthesis and the beauty of the final structures that nearly half a century ago, chemists started to investigate intertwined macrocyclic supramolecules such as rotaxanes and catenanes [4], Earlier, when the syntheses of such structures were at their infancy, the routes to such systems were troublesome. The statistical methods [5] proved to be low-yield processes. Multistep procedures [6] involving a covalent junction which is formed between two parts that are needed to stay together until the structure is complete were not convenient as well. The use of non-covalent templates thus provided a more straightforward and high-yield approach to the problem. 

Fig. 8 The two applied approaches to catenane synthesis prior to 1983. (a) The first statistical synthesis [58] relied upon the macrocyclization of a linear compound (7) in the presence of a deuterated cycloalkane (III) to achieve small amounts of the catenane V. (b) The first example [59] of directed synthesis by covalent templation was a catenane that formed after cleaving the covalent bonds around the aromatic core in compound 16. Reproduced with permission from [58] (copyright 1960 American Chemical Society), [59] (copyright 1964 Wiley-VCH)...

The early syntheses of catenanes and rotaxanes were mainly based on statistical threading approaches or on directed methodologies involving chemical conversion [30]. To obtain a catenated molecule, one ring must be closed in the presence of a... 

The breakthrough in catenane synthesis occurred when the statistical and covalent template methods were abandoned in favor of approaches that relied... 

The first catenanes and rotaxanes were constructed by either statistical [2] or directed [3] synthetic approaches. The statistical method relies [2] on the formation of small quantities of a species in which a cyclic molecule is threaded by an acyclic molecule. After experiencing appropriate covalent bond formation, these threaded species are con-... 

Early attempts at preparing catenanes relied on a more or less statistical threading approach. By cyclizing very long chains (with over 30 carbons) to make very large rings, there... 

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