Isolation and synthesis of biologically active carbazole alkaloids

Intellectual curiosity has always been one of the major driving forces leading to new advances in chemistry. At the onset of the 20th century, the fact that biaryls could be optically active even if lacking asymmetrically substituted carbon atoms arose interest, hinting at a novel type of stereomerism. It took quite a while (and some bizarre explanations)1 until in 1922 Christie and Kenner2 first correctly recognized that the phenomenon was the consequence of a hindered rotation about the aryl-aryl single bondshence termed atropisomerism by Kuhn. Still, no particular attention was initially paid to this class of stereoisomers until enantiomerically pure biaryls, such as BINAP (1),3 were found to be excellent ligands in asymmetric catalysis and until the chiral biaryl unit was recognized as the decisive structural element of many natural products (Figure 1).4,5 With the modern screening techniques and the bioassayguided search for novel compounds, the number of isolated axially chiral natural biaryls is steadily increasing.4 This class of secondary metabolites is characterized by a broad structural diversity, reaching from relatively simple molecules like the C2-symmetric biphenyl 2, which solely contains the element of axial chirality,6 to more complex compounds, like, e.g., the dimeric naphthylisoquinoline alkaloids michellamine A [(P,P)-3] and its axial epimer (i.e., its atropodiastereomer), michellamine B [(P,M)-3],7,8 which possess even three biaryl axes, of which the two outer ones are stereogenic, while * To whom correspondence should be addressed. E-mail: bringmann@ chemie.uni-wuerzburg.de; breuning@chemie.uni-wuerzburg.de. † These authors contributed equally to this work. ‡ Present address: Institute of Organic Chemistry, RWTH Aachen, Landoltweg 1, 52074 Aachen, Germany. § Present address: Kekulé Institute of Chemistry and Biochemistry, University of Bonn, Gerhard-Domagk Str. 1, 53121 Bonn, Germany. Gerhard Bringmann was born in 1951 and studied chemistry in Gie en and Münster, Germany. After his Ph.D. with Prof. B. Franck in 1978 and postdoctoral studies with Prof. Sir D. H. R. Barton in Gif-sur-Yvette (France), he passed his habilitation at the University of Münster in 1984. In 1986, he received offers for full professorships of Organic Chemistry at the Universities of Vienna and Würzburg, of which he accepted the latter in 1987. In 1998, he was offered the position of director at the Leibniz Institute of Plant Biochemistry in Halle, which he declined. His research interests focus on the field of analytical, synthetic, and computational natural product chemistry, i.e., on axially chiral biaryls. He received several prizes and awards, among them the Otto-Klung Award in chemistry (1988), the Prize for Good Teaching of the Free State of Bavaria (1999), the Adolf-Windaus Medal (2006), the Honorary Doctorate of the University of Kinshasa (2006), the Paul-J.-Scheuer Award (2007), and the Honorary Guest Professorship of Peking University (2008). Chem. Rev. 2011, 111, 563–639 563

Atroposelective total synthesis of axially chiral biaryl natural products.

Modern Graph Theory

G. Clar 6n Rule versus Hückel 4n + 2 Rule 3464 H. Hydrocarbons versus Heteroatomic Systems 3465 IV. Hidden Treasures of Kekulé Valence Structures 3466 A. Conjugated Circuits 3467 B. Innate Degree of Freedom 3470 C. Clar Structures 3472 V. Graph Theoretical Approach to Chemical Structure 3473 A. Metric 3473 B. Chemical Graphs 3473 C. Isospectral Graphs 3473 D. Embedded Graphs 3475 E. Partial Ordering 3476 VI. On Enumeration of Benzenoid Hydrocarbons 3477 VII. Kekulé Valence Structures Count 3479 A. Non-branched Cata-condensed Benzenoids 3481 B. Branched Cata-condensed Benzenoids 3482 C. Benzenoid Lattices 3482 D. Peri-condensed Benzenoids 3483 E. Miscellaneous Benzenoids 3484 F. The Approach of Platt 3485 G. Computer Programs for Calculating K 3485 H. Transfer-Matrix Method 3486 I. Use of Recursion Relations 3486 J. Use of Signed Matrices 3487 VIII. Enumeration of Conjugated Circuits 3488 IX. Approximate Approaches versus Ambitious Computations 3490

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Aromaticity of polycyclic conjugated hydrocarbons.

Let G be a graph possessing n vertices and m edges. The energy of G, denoted by E = E(G), is the sum of the absolute values of the eigenvalues of G. The connection between E and the total electron energy of a class of organic molecules is briefly outlined. Some (known) fundamental mathematical results on E are presented: the relation between E(G) and the characteristic polynomial of G, lower and upper bounds for E, especially those depending on n and m, graphs extremal with respect to E, n-vertex graphs for which E(G) > E(K n ). The characterization of the n-vertex graph(s) with maximal value of E is an open problem.

Fuji Zhang

Papers

Resistance distance and the normalized Laplacian spectrum

Plane elementary bipartite graphs

The Clar covering polynomial of hexagonal systems I

On acyclic conjugated molecules with minimal energies

On the ordering of graphs with respect to their matching numbers