The Asymmetric Universe

In 1960, John B. S. Haldane published a note in Nature [62] in which he returned to Pasteur s ideas [63] in the wake of the discovery of parity violation. Haldane is quoting Pasteur in French, but what we quote here we communicate in English translation. Haldane begins with mentioning the discovery of parity violation that has led to the notion of the asymmetrical universe. This was first enunciated by Pasteur It is inescapable that dissymmetric forces must be operative during the synthesis of the first dissymmetric natural products. ... 

Young scientists-to-be should see the universe as something of wonder, as well as something waiting to be explored and waiting to be understood. There is so much to learn about the asymmetry of our universe, but to paraphrase Albert Einstein the asymmetric universe is so amazingly comprehensible. 

It has been proposed recently [210] to use the Minkowski functionals to define the scaling length l for the 2D systems as l( = (lEuier(t)/L2)-1 2 and Is = E(t) 1, where L2 is a volume of the 2D system. A similar scaling length could be defined for the symmetric 3D systems which possess the bicontinuous interface that is, l% = (—XEuierW/ ) an(J h - E(x) l. However, this definition cannot be applied for the asymmetric blends where the change of the Euler characteristic is not universal. 

Gerard Uhommet was born in 1945 in Paris (France). He obtained his M.Sc. from the University of Paris in 1969. He carried out his Ph.D. studies under the supervision of Profs Pierre Maitte and Henri Sliwa at UPMC (P. and M. Curie University), Paris between 1970 and 1975. After a postdoctoral position at the East Anglia University in Norwich, UK, with Prof A.R. Katritzky (1976-1977), he accepted a position as Assistant Professor at UPMC, Paris. In 1985, he became Full Professor at the same university. His research interests include the development of new strategies sparing chiral auxiliaries for use in asymmetric and natural product synthesis. 

Evolution of mate-signaling in moths phylogenetic consideration and predictions from the asymmetric tracking hypothesis. In Evolution of Insect Mating Systems in Insects and Arachnids, eds. J. C. Choe and B. J. Crespi, pp. 240-256. Cambridge Cambridge University Press. 

Many methods have been developed for the enantioselective synthesis of unnatural a-amino acids. Jeff Johnston of Indiana University reports (J. Am. Chem. Soc. 125 163,2003) coupling the asymmetric alkylation of O Donnell with intramolecular radical cyclization, leading to what appears to be a general method for the enantioselective construction of indolines. 

One of the most powerful strategies for asymmetric ring construction is to desymmelrize a preformed ring. Yasamusa Hamada of Chiba University in Japan has reported (J. Am. Chem. Soc. 2004, /26, 3690) that the inexpensive diaminophosphine oxide 2 nicely catalyzes the asymmetric alkylation of the cyclohexanone carboxylate 1 to give 3. Although no examples were given, this asymmetric alkylation would probably work as well with heterocyclic P-ketoesters. 

The Sharpless asymmetric dihydroxylation has played a prominent role in enantioselecitve organic synthesis. Two groups have recently reported improvements in the procedure. Osmo E.O. Horni of the University of Oulu, Finland has found (J. Org. Chem. 2004,69,4816) that sodium chlorite is a more efficient reoxidant than is the usual K,[Fe(CN)J. Carlos A.M. Alfonso of the Instituto Superior , Lisbon has reported (J. Org. Chem. 2004,69,4381) that the asymmetric dihydroxylation can... 

The asymmetric Strecker reaction, the addition of cyanide to an aldehyde imine, is one of the better ways to prepare a-amino acids. Masakatsu Shibasaki and Motomu Kanai of the University of Tokyo... 

An interesting account and references to van t Hoff s early work can be found in The Reception of J. H. van t Hoff s Theory of the Asymmetric Carbon by H. A. M. Snelders, J. Chem. Educ. 51, 2 (1974). A century has passed since van t Hoff first published his theory, which he did-before he obtained his doctoral degree from the University of Utrecht, van t Hoff was the first recipient of the Nobel Prize in chemistry (1901) for his later work in thermodynamics and chemical kinetics. 

Fig. 1. Ribbon diagrams of Dictyostelium discoideum G-actin (Matsuura et al., 2000) and the Ascaris suum aMSP dimer (Bullock et al., 1996) at the same magnification. Actin consists of four subdomains that surround a nucleotide-binding cleft. The G-actin molecule is asymmetric, so that when it polymerizes, the filament it forms has a characteristic polarity and its two ends differ structurally. By contrast, MSP does not contain a nucleotide binding site and the polymerizing unit is a dimer in which the two MSP molecules are related by twofold rotational symmetry. Polymerization produces filaments composed of two helical subfilaments in which the dimers twofold axes are oriented perpendicular to the helix axis. Consequently, the MSP helices have no polarity and the subfilament ends are identical structurally (Bullock et al., 1998). Reproduced from The Journal of Cell Biology, 2000, vol. 149, pp. 7-12 by copyright permission of the Rockefeller University Press.

Vyacheslav V. Samoshin was born in Norilsk, Russian Federation. He graduated with an Honorable Diploma (M.S.) from Moscow State University in 1974. At the same university, he defended his Ph.D. dissertation under the supervision of academician Nikolay S. Zefirov in 1982, and his Doctor of Chemical Sciences dissertation in 1991. He worked as a researcher in the Department of Chemistry, Moscow State University, and since 1992 as professor (head of the Division of Organic Chemistry in Moscow State Academy of Fine Chemical Technology). In 1999, he took his present position as professor of chemistry at the University of the Pacific, Stockton, California. His scientific interests include molecular switches, conformational analysis, synthesis and studies of bioactive compounds, including carbohydrate mimetics, asymmetric synthesis, and synthesis and studies of crown ethers and relative compounds. 

Experimental studies permit some tests of these ideas. For example, the universality of the effect among all types of ozone isotopomers is seen in oxygen mixtures heavily enriched in and [18] and compared with theory in Figure 2.3 [12,13]. It is also seen in Figure 2.4, the points at AZPE = 0 being about 18% lower than those for the asymmetric cases. The effect of pressure on the MIF from 10 to 10 bar [16,17] has been measured and the theory tested by comparison with the data [12,13]. We note that at higher pressures all of the O3 formed is collisionally deactivated to form O3 and so the anomaly reflected in the differences in lifetimes of the symmetric and asymmetric isotopomers of O3 disappears and so the MIF disappears, experimentally and theoretically. 

The analysis of the relevant equations of the superposition approximation for the asymmetric case done in [26, 29] shows that the universality n t) oc violated for J = 3 in this case instead of n t) oc one... 

Vince S. C. Yeh received his B.S. degree (1994) from the University of British Columbia where he participated in undergraduate research under the late Professor L. Weiler. He completed Ph.D. (2001) from the University of Alberta under the guidance of Professor D. L. J. Clive, where he studied the asymmetric syntheses of alkaloids. After postdoctoral research (2003) with Professor B. M. Trost at Stanford University on asymmetric aldol catalysts, he joined Abbott Laboratories as a senior research chemist working in the area of metabolic diseases. His research interests include drug discovery, asymmetric synthesis, and natural products. 

Lynn Power was born in Co. Wexford, Ireland. She completed a B.Sc. degree at the National University of Ireland, Maynooth in 2004, including a final year research project with Dr. Frances Heaney. She was the recipient of the Kathleen Lonsdale Prize for the best student graduating in chemistry. She then carried out Ph.D. work at the University of St. Andrews in the area of asymmetric synthesis using chiral dioxolanones under the supervision of Dr. Alan Aitken. 

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