Son T. Nguyen

Catalytic, Nucleophilic Allylation of Aldehydes with Allyl Acetate

A new catalytic allylation of aldehydes has been developed that employs allyl acetate as the allylating reagent. Under catalysis by ruthenium trichloride (3 mol %) in the presence of carbon monoxide (30 psi), water (1.5 equiv), and triethylamine (0.1 equiv), a wide range of aromatic, olefinic, and aliphatic aldehydes are efficiently allylated under mild conditions (70 degrees C, 24-48 h). The stoichiometric byproducts of this reaction are carbon dioxide and acetic acid.

ASYMMETRIC SYNTHESIS OF THE ABCD RING SYSTEM OF DAPHNILACTONE B VIA A TANDEM, DOUBLE INTRAMOLECULAR, [4+2]/[3+2] CYCLOADDITION STRATEGY

An asymmetric synthesis of the ABCD ring system of daphnilactone B is described. The synthesis features a tandem, double intramolecular, [4+2]/[3+2] cycloaddition of a highly functionalized, enantiomerically enriched nitroalkene to generate a pentacyclic nitroso acetal. The cycloaddition establishes six contiguous stereogenic centers including the critical CD ring junction that bears two quaternary stereogenic centers. Hydrogenolysis of the nitroso acetal followed by amide reduction and cyclization provided the AB rings. The methyl substituent on the A ring was installed in the correct configuration via hydrogenation of an exocyclic olefin in the final step.

Characterizing and Adapting the Consistency-Latency Tradeoff in Distributed Key-Value Stores

The CAP theorem is a fundamental result that applies to distributed storage systems. In this article, we first present and prove two CAP-like impossibility theorems. To state these theorems, we present probabilistic models to characterize the three important elements of the CAP theorem: consistency (C), availability or latency (A), and partition tolerance (P). The theorems show the un-achievable envelope, that is, which combinations of the parameters of the three models make them impossible to achieve together. Next, we present the design of a class of systems called Probabilistic CAP (PCAP) that perform close to the envelope described by our theorems. In addition, these systems allow applications running on a single data center to specify either a latency Service Level Agreement (SLA) or a consistency SLA. The PCAP systems automatically adapt, in real time and under changing network conditions, to meet the SLA while optimizing the other C/A metric. We incorporate PCAP into two popular key-value stores: Apache Cassandra and Riak. Our experiments with these two deployments, under realistic workloads, reveal that the PCAP systems satisfactorily meets SLAs and perform close to the achievable envelope. We also extend PCAP from a single data center to multiple geo-distributed data centers.

AMETHYST: a system for mining and exploring topical hierarchies of heterogeneous data

In this demo we present AMETHYST, a system for exploring and analyzing a topical hierarchy constructed from a heterogeneous information network (HIN). HINs, composed of multiple types of entities and links are very common in the real world. Many have a text component, and thus can benefit from a high quality hierarchical organization of the topics in the network dataset. By organizing the topics into a hierarchy, AMETHYST helps understand search results in the context of an ontology, and explain entity relatedness at different granularities. The automatically constructed topical hierarchy reflects a domain-specific ontology, interacts with multiple types of linked entities, and can be tailored for both free text and OLAP queries.

Quantitative Analysis of Consistency in NoSQL Key-Value Stores

The promise of high scalability and availability has prompted many companies to replace traditional relational database management systems RDBMS with NoSQL key-value stores. This comes at the cost of relaxed consistency guarantees: key-value stores only guarantee eventual consistency in principle. In practice, however, many key-value stores seem to offer stronger consistency. Quantifying how well consistency properties are met is a non-trivial problem. We address this problem by formally modeling key-value stores as probabilistic systems and quantitatively analyzing their consistency properties by statistical model checking. We present for the first time a formal probabilistic model of Apache Cassandra, a popular NoSQL key-value store, and quantify how much Cassandra achieves various consistency guarantees under various conditions. To validate our model, we evaluate multiple consistency properties using two methods and compare them against each other. The two methods are: 1 an implementation-based evaluation of the source code; and 2 a statistical model checking analysis of our probabilistic model.

Catalytic Nucleophilic Allylation Driven by the Water–Gas Shift Reaction

The ruthenium-catalyzed allylation of aldehydes with allylic pro-nucleophiles has been demonstrated to be an efficient means to form carbon-carbon bonds under mild conditions. The evolution of this reaction from the initial serendipitous discovery to its general synthetic scope is detailed, highlighting the roles of water, CO, and amine in the generation of a more complete catalytic cycle. The use of unsymmetrical allylic pro-nucleophiles was shown to give preferential product formation through the modulation of reaction conditions. Both (E)-cinnamyl acetate and vinyl oxirane were efficiently used to form the anti-branched products (up to >20:1 anti/syn) and E-linear products (up to >20:1 E/Z) in high selectivity with aromatic, α,β-unsaturated, and aliphatic aldehydes, respectively. Attempts to render the reaction enantioselective are highlighted and include enantioenrichment of up to 75:25 for benzaldehyde.