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The Pd-catalyzed coupling of N-allylguanidines or N-allylureas with O-benzoylhydroxylamine derivatives affords cyclic guanidines or cyclic ureas bearing dialkylaminomethyl groups. The desired products are obtained in good yield, and substrates bearing substituents at the allylic position are transformed with moderate diastereoselectivity. The mechanism of these reactions appears to involve anti-aminopalladation of the alkene, followed by a rare sp(3)C–sp(3)N bond-forming reductive elimination from an alkylpalladium complex that contains β-hydrogen atoms.

Use of peer instruction and facilitation has surged in undergraduate education at large colleges and universities in recent years. Studies on peer instruction have been directed primarily at student learning gains and affective outcomes among the facilitators. For peer instructors, the relationship between their teaching effectiveness and their foundational content knowledge is assumed but understudied. In an effort to promote instructional coherence (i.e., instructional same-pageness) in the introductory organic chemistry program at the University of Michigan, we observed peer-led study group facilitators’ involvement in their study groups (as teachers of groups of 6–12 students) and in a companion course (as learners) designed to reinforce and enhance their content knowledge. Audiovisual recordings of the facilitators in both the companion course and, for ten of them, leading their study groups, were captured over each of the two week periods covering the topics of stereochemistry and also conformational analysis. Recordings were subsequently coded for topic and correctness in presentation of subject matter. Errors made in either study group or the companion course were investigated for error resolution (corrected or uncorrected), source of error, and propagation of corrected errors. Analysis of recordings revealed that facilitators who have their own errors corrected in the companion course, or observe their peers’ errors corrected in the companion course, correctly describe these concepts in study groups. On examining errors made by facilitators when they are leading study group sessions, a backwards analysis showed consistently that either the topics had not been addressed in the antecedent companion course, or the facilitator was not actively engaged with the discussion when the topics were being discussed. These findings have implications to inform not only our own implementation of peer-led study groups, but also those interested in designing subject matter companion courses for peer leaders in other instructional settings.

Modified reaction conditions that facilitate Pd-catalyzed alkene carboamination reactions of electron-deficient nitrogen nucleophiles are reported. Pent-4-enylamine derivatives bearing N-tosyl or N-trifluoroacetyl groups are coupled with aryl triflates to afford substituted pyrrolidines in good yield. These reactions proceed via a mechanism involving anti-aminopalladation of the alkene, which differs from previously reported analogous reactions of N-aryl and N-boc pentenylamines. The application of these conditions to a formal synthesis of (±)-aphanorphine is also described.

Palladium-catalyzed carboamination reactions of N-allylguanidines bearing cleavable N-cyano or N-arylsulfonyl protecting groups are described. The reactions afford cyclic guanidine products in good yield, and transformations of substrates bearing internal alkenes proceed with high diastereoselectivity. Deuterium labeling studies indicate these transformations proceed via anti-aminopalladation pathways.

Modified reaction conditions that facilitate Pd-catalyzed alkene carboamination reactions of electron-deficient nitrogen nucleophiles are reported. Pent-4-enylamine derivatives bearing N-tosyl or N-trifluoroacetyl groups are coupled with aryl triflates to afford substituted pyrrolidines in good yield. These reactions proceed via a mechanism involving anti-aminopalladation of the alkene, which differs from previously reported analogous reactions of N-aryl and N-boc pentenylamines. The application of these conditions to a formal synthesis of (±)-aphanorphine is also described.

Mycobacteriophages are viruses that infect mycobacterial hosts such as Mycobacterium smegmatis and Mycobacterium tuberculosis. All mycobacteriophages characterized to date are dsDNA tailed phages, and have either siphoviral or myoviral morphotypes. However, their genetic diversity is considerable, and although sixty-two genomes have been sequenced and comparatively analyzed, these likely represent only a small portion of the diversity of the mycobacteriophage population at large. Here we report the isolation, sequencing and comparative genomic analysis of 18 new mycobacteriophages isolated from geographically distinct locations within the United States. Although no clear correlation between location and genome type can be discerned, these genomes expand our knowledge of mycobacteriophage diversity and enhance our understanding of the roles of mobile elements in viral evolution. Expansion of the number of mycobacteriophages grouped within Cluster A provides insights into the basis of immune specificity in these temperate phages, and we also describe a novel example of apparent immunity theft. The isolation and genomic analysis of bacteriophages by freshman college students provides an example of an authentic research experience for novice scientists.