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Volumn 64, Issue 36, 2008, Pages 8464-8475

Integrating replication processes with mechanically interlocked molecular architectures

Author keywords

Kinetics; Molecular recognition; Rotaxanes; Self replication

Indexed keywords

MACROCYCLIC COMPOUND; ROTAXANE;

EID: 47949121066     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tet.2008.05.049     Document Type: Article
Times cited : (37)

References (144)
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    • Until the advent of synthetic strategies that exploited molecular recognition for the construction of mechanically interlocked architectures, the study of such systems was confined to more theoretical aspects of such assembly. See:
    • Until the advent of synthetic strategies that exploited molecular recognition for the construction of mechanically interlocked architectures, the study of such systems was confined to more theoretical aspects of such assembly. See:. Walba D.M. Tetrahedron 41 (1985) 3161-3212
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    • The [1·3] complex has a larger association constant than the [1·2] complex despite the fact that both 2 and 3 having the same binding site. The slow exchange on the chemical shift time scale exhibited by the [1·3] complex suggests that the on and off rates for this complex are significantly lower than those for the [1·2] complex. This change in the on and off rates probably arises from a steric barrier imposed by a close complementarity between the mean free path through the cavity of macrocycle 1 and the phenylethynyl substituents present in 3, rather than a greatly altered intrinsic binding of the pyridone ring to the macrocycle. The small size of macrocycle 1 is evident in other situations in this work (cf. complex [1·10]). For a discussion of slippage and constrictive binding, see:. Vögtle F., Stoddart J.F., and Shibasaki M. (Eds), VCH, Weinheim
    • The [1·3] complex has a larger association constant than the [1·2] complex despite the fact that both 2 and 3 having the same binding site. The slow exchange on the chemical shift time scale exhibited by the [1·3] complex suggests that the on and off rates for this complex are significantly lower than those for the [1·2] complex. This change in the on and off rates probably arises from a steric barrier imposed by a close complementarity between the mean free path through the cavity of macrocycle 1 and the phenylethynyl substituents present in 3, rather than a greatly altered intrinsic binding of the pyridone ring to the macrocycle. The small size of macrocycle 1 is evident in other situations in this work (cf. complex [1·10]). For a discussion of slippage and constrictive binding, see:. Fyfe M.C.T., Raymo F.M., and Stoddart J.F. In: Vögtle F., Stoddart J.F., and Shibasaki M. (Eds). Stimulating Concepts in Chemistry (2000), VCH, Weinheim 211-220
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    • Several groups have exploited the use of amides for the construction of rotaxanes over the past 15 years. For some examples, see:
    • Several groups have exploited the use of amides for the construction of rotaxanes over the past 15 years. For some examples, see:
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    • See Ref. 18c.
    • See Ref. 18c.
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    • note
    • During the course of this work, we also discovered that nitrones can bind macrocycle 1. Therefore, we designed nitrone 5 in order to prevent pseudorotaxane formation between macrocycle 1 and the nitrone.
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    • note
    • The stereochemical labels trans and cis refer to the relative stereochemistry in the cycloadduct of the proton derived from the nitrone with respect to the ring junction protons (derived from the maleimide). In the trans diastereoisomer, the proton derived from the nitrone is on the opposite face of the fused ring system as the ring junction protons derived from the maleimide. In the cis diastereoisomer, the proton derived from the nitrone is on the same face of the fused ring system as the ring junction protons derived from the maleimide.
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    • note
    • 3. Under these conditions, exchange between bound and unbound species is slow on the chemical shift time scale and, therefore, a crude estimate of the association constant can be obtained simply by integrating resonances arising from the two species.
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    • note
    • The dipolar cycloaddition between a nitrone and an N-aryl maleimide is rather insensitive to electronic effects and usually gives a trans/cis ratio between 2.7:1 and 3.3:1.
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    • note
    • 3 of this pseudorotaxane shows broad resonances at 25 °C as a result of intermediate exchange on the chemical shift time scale. Therefore, the ROESY experiment was performed at -30 °C (slow exchange limit).
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    • Altered reactivity of functional groups incorporated within mechanically interlocked structures is a well-established phenomenon. For some examples, see:
    • Altered reactivity of functional groups incorporated within mechanically interlocked structures is a well-established phenomenon. For some examples, see:
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    • note
    • -1 higher than that for the reaction of 15 in the absence of macrocycle. Whilst the absolute value of this difference is unlikely to be correct at this low level of theory, it does support, at least qualitatively, the conclusion that binding of the macrocycle introduces a supramolecular steric effect into the system.
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.