Synthesis, asymmetric light

FIGURE 22.21 The mechanism of photophosphorylation. Photosynthetic electron transport establishes a proton gradient that is tapped by the CFiCFo ATP synthase to drive ATP synthesis. Critical to this mechanism is the fact that the membrane-bound components of light-induced electron transport and ATP synthesis are asymmetrical with respect to the thylakoid membrane so that vectorial discharge and uptake of ensue, generating the proton-motive force. 

In a special case of this type of asymmetric synthesis, a compound (47) with achiral molecules, but whose crystals are chiral, was converted by UV light to a single enantiomer of a chiral product (48). ... 

As mentioned in Section 1.2, the presence of an asymmetric carbon is neither a necessary nor a sufficient condition for optical activity. Each enantiomer of a chiral molecule rotates the plane of polarized light to an equal degree but in opposite directions. A chiral compound is optically active only if the amount of one enantiomer is in excess of the other. Measuring the enantiomer composition is very important in asymmetric synthesis, as chemists working in this area need the information to evaluate the asymmetric induction efficiency of asymmetric reactions. 

S. Jin, M. Jang, andH. Suh, Synthesis and characterization of highly luminescent asymmetric polyfp-phenylene vinylene) derivatives for light-emitting diodes, Chem. Mater., 14 643-650, 2002. 

The asymmetric synthesis thus carried out is also known as partial asymmetric synthesis and to distinguish it from that where no optically active compound is used but in its place circularly polarized light is used, we use the term absolute asymmetric synthesis. 

Since the early times of stereochemistry, the phenomena related to chirality ( dis-symetrie moleculaire, as originally stated by Pasteur) have been treated or referred to as enantiomericaUy pure compounds. For a long time the measurement of specific rotations has been the only tool to evaluate the enantiomer distribution of an enantioimpure sample hence the expressions optical purity and optical antipodes. The usefulness of chiral assistance (natural products, circularly polarized light, etc.) for the preparation of optically active compounds, by either resolution or asymmetric synthesis, has been recognized by Pasteur, Le Bel, and van t Hoff. The first chiral auxiliaries selected for asymmetric synthesis were alkaloids such as quinine or some terpenes. Natural products with several asymmetric centers are usually enantiopure or close to 100% ee. With the necessity to devise new routes to enantiopure compounds, many simple or complex auxiliaries have been prepared from natural products or from resolved materials. Often the authors tried to get the highest enantiomeric excess values possible for the chiral auxiliaries before using them for asymmetric reactions. When a chiral reagent or catalyst could not be prepared enantiomericaUy pure, the enantiomeric excess (ee) of the product was assumed to be a minimum value or was corrected by the ee of the chiral auxiliary. The experimental data measured by polarimetry or spectroscopic methods are conveniently expressed by enantiomeric excess and enantiomeric... 

We have demonstrated the enantioselective synthesis of near-enantiopure compounds by asymmetric photodegradation of racemic pyrimidyl alkanol 2c by circularly polarized light followed by asymmetric autocatalysis. This is the first example of asymmetric autocatalysis triggered directly by a chiral physical factor CPL. 

More recently, in light of the development of the Sharpless asymmetric dihydroxylation protocol [20], we have approached the synthesis of diols such as 14 (Scheme 2) from the alkene. Thus, treatment of the alkenyl D-glucosides 15 vmder the conditions of the Sharpless dihydroxylation gave a range of diols 16 with varying diastereoisomeric excesses (Table 1). One of these mixtures of diols, upon recrystallization, yielded the pure diastereoisomer, namely the diol 14. This procedure now gives a very rapid and efficient entry into one of the precursor diols for the synthesis of the optically-pure epoxides [21]. 

Asymmetric Synthesis with Circularly Polarized Light... 

Although photochemical cycloadditions can prove difficult to scale up, they do offer access to cycloadducts not directly accessible by other methods.480 481 The initial studies into asymmetric synthesis by photochemical means were in the solid phase or organized assemblies, and few examples were known in solution 482 483 Circular polarized light, a chiral agent, has the potential to induce asymmetric synthesis, although useful ee s have not yet been obtained.481... 

The synthetic utility of the photolytic decomposition pathway of pyrrolo[3,4-J]-1,2,3-triazole derivatives has been realised in the asymmetric synthesis of (—)-quinocarcin. Thus, the triazine (62) was irradiated using a mercury light source to give aziridine (63) in 90% yield via loss of nitrogen <93JA10742>. 

An interesting approach is a method that uses the modulation of the degree of circular polarization (e.g., between pure 1-cpl and linearly polarized light) to determine fast isomerization kinetics [71]. However, preliminary results on [Co(ox)(phen)2] and rhodamin 6G 14 were not followed by the announced full papers, and the arcticle is rarely cited. In principle the concept may be used to determine interconversion and the CD spectra of rotamers (like 14) which are the reactants in asymmetric synthesis (see Sec. II.C.). 

Circularly polarized light (CPL), often used as a source for the absolute asymmetric synthesis of chiral compounds [76-79], can be used as a trigger... 

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