Gray Whales (Eschrichtius robustus) Off Sakhalin Island, Russia: Seasonal And Annual Patterns Of Occurrence

The annual return, seasonal occurrence, and site fidelity of Korean-Okhotsk or western gray whales on their feeding grounds off northeastern Sakhalin Island, Russia, were assessed by boat-based photo-identification studies in 1994-1998. A total of 262 pods were observed, ranging in size from 1 to 9 whales with an overall mean of 2.0'. Sixty-nine whales were individually identified, and a majority of all whales (71.0%) were observed in multiple years. Annual sighting frequencies ranged from 1 to 18 d, with a mean of 5.4 d. The percentage of whales re-identified from previous years showed a continuous annual increase, reaching 87.0% by the end of the study. Time between first and last sighting of identified individuals within a given year was 1-85 d, with an overall mean of 40.6 d. Annual calf proportions ranged from 4.3% (1997) to 13.2% (1998), and mother-calf separations generally occurred between July and September. The seasonal site fidelity and annual return of whales to this part of the Okhotsk Sea emphasize its importance as a primary feeding ground for this endangered population.

I. Development of the In Situ Reductive Ozonolysis of Alkenes with Tertiary Amine N-Oxides. II. Progress toward the Asymmetric Synthesis of Peroxyplakoric Acid A3.

Ozone, first discovered in the mid 1800’s, is a triatomic allotrope of oxygen that is a powerful oxidant. For over a century, research has been conducted into the synthetic application and mechanism of reactions of ozone with organic compounds. One of the major areas of interest has been the ozonolysis of alkenes. The production of carbonyl compounds is the most common synthetic application of ozonolysis. The generally accepted mechanism developed by Rudolf Criegee for this reaction involves the 1,3-electrocyclic addition of ozone to the π bond of the alkene to form a 1,2,3-trioxolane or primary ozonide. The primary ozonide is unstable at temperatures above -100 °C and undergoes cycloreversion to produce the carbonyl oxide and carbonyl intermediates. These intermediates then recombine in another 1,3-electrocyclic addition step to form the 1,2,4-trioxolane or final ozonide. While the final ozonide is often isolable, most synthetic applications of ozonolysis require a subsequent reductive or oxidative step to form the desired carbonyl compound. During investigations into the nucleophilic trapping of the reactive carbonyl oxide, it was discovered that when amines were used as additives, an increased amount of reaction time was required in order to consume all of the starting material. Surprisingly, significant amounts of aldehydes and a suppression of ozonide formation also occurred which led to the discovery that amine N-oxides formed by the ozonation of the amine additives in the reaction were intercepting the carbonyl oxide. From the observed production of aldehydes, our proposed mechanism for the in situ reductive ozonolysis reaction with amine N-oxides involves the nucleophilic trapping of the carbonyl oxide intermediate to produce a zwitterionic adduct that fragments into 1O2, amine and the carbonyl thereby avoiding the formation of peroxidic intermediates. With the successful total syntheses of peroxyacarnoates A and D by Dr. Chunping Xu, the asymmetric total synthesis of peroxyplakorate A3 was investigated. The peroxyplakoric acids are cyclic peroxide natural products isolated from the Plakortis species of marine sponge that have been found to exhibit activity against malaria, cancer and fungi. Even though the peroxyplakorates differ from the peroxyacarnoates in the polyunsaturated tail and the head group, the lessons learned from the syntheses of the peroxyacarnoates have proven to be valuable in the asymmetric synthesis of peroxyplakorate A3. The challenges for the asymmetric synthesis of peroxyplakorate A3 include the stereospecific formation of the 3-methoxy-1,2-dioxane core with a propionate head group and the introduction of oxidation sensitive dienyl tail in the presence of a reduction sensitive 1,2-dioxane core. It was found that the stereochemistry of two of the chiral centers could be controlled by an anti-aldol reaction of a chiral propionate followed by the stereospecific intramolecular cyclization of a hydroperoxyacetal. The regioselective ozonolysis of a 1,2-disubstituted alkene in the presence of a terminal alkyne forms the required hydroperoxyacetal as a mixture of diastereomers. Finally, the dienyl tail is introduced by a hydrometallation/iodination of the alkyne to produce a vinyl iodide followed by a palladium catalyzed coupling reaction. While the coupling reaction was unsuccessful in these attempts, it is still believed that the intramolecular cyclization to introduce the 1,2-dioxane core could prove to be a general solution to many other cyclic peroxides natural products.

Rhodium-Catalyzed Hydroboration: Directed Asymmetric Desymmetrization

Rhodium-catalyzed asymmetric hydroboration in conjunction with directing groups can be used control relative and absolute stereochemistry. Hydroboration has the potential to create new C–C, C–O, and C–N bonds from an intermediate C–B bond with retention of stereochemistry. Desymmetrization resulting in the loss of one or more symmetry elements can give rise to molecular chirality, i.e., the conversion of a prochiral molecule to one that is chiral. Unsaturated amides and esters hold the potential for two-point binding to the rhodium catalyst and have been shown to direct the regiochemistry and impact stereochemistry in asymmetric hydroborations of acyclic β,γ-unsaturated substrates. In the present study, the pendant amide functionality directs the hydroboration cis in the cyclic substrates studied; the corresponding ester substrates do so to a lesser extent. The enantioselectivity is determined by regioselective addition to the re or si site of the rhodium-complexed alkene. The effect of catalyst, ligand and borane on the observed diastereoselectivity and enantioselectivity for a variety of cyclopentenyl ester and amide substrates is discussed.

Planning “Discrete” Movements Using a Continuous System: Insights from a Dynamic Field Theory of Movement Preparation

The timed-initiation paradigm developed by Ghez and colleagues (1997) has revealed two modes of motor planning: continuous and discrete. Continuous responding occurs when targets are separated by less than 60° of spatial angle, and discrete responding occurs when targets are separated by greater than 60°. Although these two modes are thought to reflect the operation of separable strategic planning systems, a new theory of movement preparation, the Dynamic Field Theory, suggests that two modes emerge flexibly from the same system. Experiment 1 replicated continuous and discrete performance using a task modified to allow for a critical test of the single system view. In Experiment 2, participants were allowed to correct their movements following movement initiation (the standard task does not allow corrections). Results showed continuous planning performance at large and small target separations. These results are consistent with the proposal that the two modes reflect the time-dependent “preshaping” of a single planning system.