Screw sense

The preparation of helically well-ordered polymers with stable screw-sense, which is able to be transmitted to newly formed polymer main-chains effectively, is highly desired for the development of new methodology for the synthesis of optically active helical polymers. An aromatizing polymerization of 1,2-diisocyanobenzenes is promoted by methylpalladium(II) complexes, producing poly(quinoxaline-2,3-diyl)s.146-148 The polymerization proceeds with successive insertion of the two isocyano groups of the diisocyanobenzene to the carbon palladium bond of... 

Polyacetylenes are the most important class of synthetic polymers containing conjugated carbon-carbon double bonds. Some optically active monomers have been used with the following conclusions. Polymers of 1-alkynes having a branched side-chain assume in solution a helical conformation. A chiral side-chain induces a predominant screw sense in these helices. In particular, for alkyl branching, it has been shown that (S) monomers lead to a left-handed screw sense. 

Preferential Screw Sense Helical Ordering of Polysilanes... 

Preferential Screw Sense Homopolymers with Enantiopure Chiral Side Chains... 

Optically Active Polysilanes with Diastereomeric Helidties Containing Opposite Screw Senses and Different Screw Pitches... 

Copolymers with Preferential Screw Sense and Sergeants-and-Soldiers Principle... 

Switching Preferential Screw Sense by Helix-Helix Transition... 

Preferential screw sense helix induced by chiral side groups and/or chiral chemical influence... 

Illustrations of coincident CD and UV absorptions for chromophoric main chain screw sense and (b) equal proportion of P and M screw senses. 

The cut-and-paste technique has two steps (i) M (or P) screw-sense-selective photolysis at the longer kmax region in CC14 to form P (or M) screw sense telomers with Si-Cl termini, and (ii) Na-mediated recondensation of the telomers in hot toluene. Formation of an optically active helical polysilane with an almost single screw sense was evidenced by significant changes in the UV and CD spectra after the cut-and-paste technique, as shown in Figure 4.6b. 

This knowledge and understanding may be helpful to characterize local conformations of other optically active polysilanes in solution. For example, poly(methyl-(-)-(3-pinanylsilane) [(+)-7 Mw = 10,200] prepared by Shinohara and co-workers.281 showed a bisignate CD band at 280 and 303 nm, associated with a broad UV absorption at 300 nm in chloroform at 15°C. Since the spectroscopic features are quite similar to those of i,28d-28e it is possible that the main chain in 7 may contain diastereomeric helical motifs with opposite screw senses and different screw pitches. 

On the other hand, noticeable cooperative preferential screw sense induction was reported in rodlike polysilane copolymers bearing (.S )-2-mcthylbutyl and 2-methylpropyl groups (10) and (R)-2-melhylbutyl and 2-methylpropyl groups (11) in isooctane (Chart 4.3). Since the UV-CD spectral features of the polysilane copolymers are almost identical with those of 4-6 and the Xmax varies sensitively with changes in the molar fraction of chiral substituents and temperature,28 the copolymer systems are suitable for testing the sergeants-and-soldiers phenomenon by their CD-UV spectra. 

Another significant cooperativity effect in preferential helical screw sense optically active copolymers is the majority rule phenomenon.18bl8q In this case, the screw sense of a helical main chain with unequal proportions of opposite chirality enantiopure chiral side groups is controlled by the enantiomeric excess only. Since this phenomenon was first reported from poly-a-olefins made of vinyl co-monomers bearing nonenantiopure chiral moieties by Green et al.8b and Pino et al.,16b this majority rule has been established in... 

Kira and co-workers described the first single-crystal X-ray structure, CD, and UV spectra of hexasilane oligomers with preferential screw sense induced by... 

We also reported an intriguing chiral termini effect in rodlike poly(n-hexyl-(2-methylpropyl)silane) with (5)-2-me(hylbu(yl termini (15).28g Although the value of gabs is only +1 x 10-5, which indicates a very weak preferential screw sense in 15, it is noted that the preferential screw sense of 15 was opposite to that of 4, bearing the same (5)-2-me(hylbutyl side groups.28d,28f,28k... 

In this section, we comprehensively focused on the controlled synthesis, chiroptical characterization, and manipulation of optically active poly(dialkyl-silane)s. Although many artificial polymers adopting preferential screw sense... 

By contrast, in the CD spectrum of the p derivative (39), no bands were observed even at —80°C, as shown in Figure 4.19b. This is because the Cotton band of the p derivative is canceled by an oppositely signed CD band originating in an equivalent proportion of opposite screw sense helical segments (which may be referred to as masked helicity or masked circular dichro-ism ). The difference between the helical conformations of m and p derivatives may be due to the degree of steric hindrance of (S>2-methylbutoxyphenyl rings, since the p derivative may have enough space to freely rotate the... 

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