Enantioselective synthesis of pyrroloindolines and tryptophan derivatives by an asymmetric protonation reaction

Pyrroloindoline and unnatural tryptophan motifs are important targets for synthesis based on their incorporation into a diverse array of biologically active natural products. Both types of alkaloids have also found applications as chiral catalysts and tryptophan derivatives are commonly employed as biological probes. On account of their applications, these frameworks have inspired the development of numerous enantioselective, catalytic reactions. In particular, the past few years have witnessed an impressive number of novel approaches for pyrroloindoline formation.

The first project described herein involves our contribution to pyrroloindoline research. We have developed an (R)-BINOL•SnCl₄-catalyzed formal (3 + 2) cycloaddition reaction between 3-substituted indoles and 2-amidoacrylates that affords pyrroloindoline-2-carboxylates bearing an all-carbon quaternary center. Mechanistic studies have elucidated that the enantiodetermining step is a highly face-selective catalyst-controlled protonation reaction. The subsequent application of this asymmetric protonation strategy to the synthesis of a variety of enantioenriched tryptophan derivatives is also discussed.

Legal dimensions of the Chinese experience in Los Angeles, 1860-1880

On October 24, 1871, a massacre of eighteen Chinese in Los Angeles brought the small southern California settlement into the national spotlight. Within a few days, news of this “night of horrors” was reported in newspapers across the country. This massacre has been cited in Asian American narratives as the first documented outbreak of ethnic violence against a Chinese community in the United States. This is ironic because Los Angeles’ small population has generally placed it on the periphery in historical studies of the California anti-Chinese movement. Because the massacre predated Los Angeles’ organized Chinese exclusion movements of the late 1870s, it has often been erroneously dismissed as an aberration in the history of the city.

The violence of 1871 was an outburst highlighting existing community tensions that would become part of public debate by decade’s close. The purpose of this study is to insert the massacre into a broader context of anti-Chinese sentiments, legal discrimination, and dehumanization in nineteenth century Los Angeles. While a second incident of widespread anti-Chinese violence never occurred, brutal attacks directed at Chinese small businessmen and others highlighted continued community conflict. Similarly, economic rivalries and concerns over Chinese prostitution that underlay the 1871 massacre were manifest in later campaigns of economic discrimination and vice suppression that sought to minimize Chinese influence within municipal limits. An analysis of the massacre in terms of anti-Chinese legal, social and economic strategies in nineteenth-century Los Angeles will elucidate these important continuities.