Regioselective Synthesis of Benzimidazolones via Cascade C–N Coupling of Monosubstituted Ureas

A direct method for the regioselective construction of benzimidazolones is reported wherein a single palladium catalyst is employed to couple monosubstituted urea substrates with differentially substituted 1,2-dihaloaromatic systems. In this method, the catalyst is able to promote a cascade of two discrete chemoselective C–N bond-forming processes that allows the highly selective and predictable formation of complex heterocycles from simple, readily available starting materials.National Institutes of Health (U.S.) (Award GM58160)National Institutes of Health (U.S.) (Award GM099817)Lanxess CorporationMassachusetts Institute of Technology. Undergraduate Research Opportunities Progra

Critical Perspective: Named Reactions Discovered and Developed by Women

Named organic reactions. As chemists, we’re all familiar with them: who can forget the Diels−Alder reaction? But how much do we know about the people behind the names? For example, can you identify a reaction named for a woman? How about a reaction discovered or developed by a woman but named for her male adviser? Our attempts to answer these simple questions started us on the journey that led to this Account. We introduce you to four reactions named for women and nine reactions discovered or developed by women. Using information obtained from the literature and, whenever possible, through interviews with the chemists themselves, their associates, and their advisers, we paint a more detailed picture of these remarkable women and their outstanding accomplishments. Some of the women you meet in this Account include Irma Goldberg, the only woman unambiguously recognized with her own named reaction. Gertrude Maud Robinson, the wife of Robert Robinson, who collaborated with him on several projects including the Piloty−Robinson pyrrole synthesis. Elizabeth Hardy, the Bryn Mawr graduate student who discovered the Cope rearrangement. Dorothee Felix, a critical member of Albert Eschenmoser’s research lab for over forty years who helped develop both the Eschenmoser−Claisen rearrangement and the Eschenmoser−Tanabe fragmentation. Jennifer Loebach, the University of Illinois undergraduate who was part of the team in Eric Jacobsen’s lab that discovered the Jacobsen−Katsuki epoxidation. Keiko Noda, a graduate student in Tsutomu Katsuki’s lab who also played a key role in the development of the Jacobsen−Katsuki epoxidation. Lydia McKinstry, a postdoc in Andrew Myers’s lab who helped develop the Myers asymmetric alkylation. Rosa Lockwood, a graduate student at Boston College whose sole publication is the discovery of the Nicholas reaction. Kaori Ando, a successful professor in Japan who helped develop the Roush asymmetric alkylation as a postdoc at MIT. Bianka Tchoubar, a critically important member of the organic chemistry community in France who developed the Tiffeneau−Demjanov rearrangement. The accomplishments of the women in this Account illustrate the key roles women have played in the discovery and development of reactions used daily by organic chemists around the world. These pioneering chemists represent the vanguard of women in the field, and we are confident that many more of the growing number of current and future female organic chemists will be recognized with their own named reactions

Genetic divergence of rubber tree estimated by multivariate techniques and microsatellite markers

Genetic diversity of 60 Hevea genotypes, consisting of Asiatic, Amazonian, African and IAC clones, and pertaining to the genetic breeding program of the Agronomic Institute (IAC), Brazil, was estimated. Analyses were based on phenotypic multivariate parameters and microsatellites. Five agronomic descriptors were employed in multivariate procedures, such as Standard Euclidian Distance, Tocher clustering and principal component analysis. Genetic variability among the genotypes was estimated with 68 selected polymorphic SSRs, by way of Modified Rogers Genetic Distance and UPGMA clustering. Structure software in a Bayesian approach was used in discriminating among groups. Genetic diversity was estimated through Nei's statistics. The genotypes were clustered into 12 groups according to the Tocher method, while the molecular analysis identified six groups. In the phenotypic and microsatellite analyses, the Amazonian and IAC genotypes were distributed in several groups, whereas the Asiatic were in only a few. Observed heterozygosity ranged from 0.05 to 0.96. Both high total diversity (HT' = 0.58) and high gene differentiation (G st' = 0.61) were observed, and indicated high genetic variation among the 60 genotypes, which may be useful for breeding programs. The analyzed agronomic parameters and SSRs markers were effective in assessing genetic diversity among Hevea genotypes, besides proving to be useful for characterizing genetic variability