Synthesis of Valuable Optically Active Compounds From Versatile Natural Products Using Biocatalyst

Transition Metal/Lewis Acid Catalyzed Reactions of Zerumbone for Diverse Molecular Motifs

“…[3] Strategies in DOS for construction of small-molecule libraries of biological relevance with skeletal and stereochemical diversity comprise build/couple/pair (B/C/P), ringdistortion, complexity-generation, cascade and multicomponent reactions. [4][5][6][7][8][9][10][11] DOS can be extended to even NP extracts by direct chemical derivatization to produce diversity-enhanced extracts. [12] Abundant natural products provides an opportunity for derivatization using the versatile transition-metal catalyzed methodologies that enable carbon-carbon bond formations in a combinatorial chemistry approach to afford diverse molecular frameworks.…”

“…[49] Due to its ready availability and accessibility, zerumbone stands as a sustainable material for DOS. [6,47] Kitayama et al, has published pioneering contributions in successful diversification of zerumbone, they reported six natural product-like skeletons from zerumbone by applying the concept of DOS. [50] An allene type zerumbone derivative, 12-membered ring, by a Doering-LaFlamme allene method was believed to be an important building block that culminates in synthesis of BC ring of paclitaxel (Scheme 2).…”

Remarkable Potential of Zerumbone to Generate a Library with Six Natural Product-like Skeletons by Natural Material-Related Diversity-Oriented Synthesis

“…Readily available small natural products are suitable as starting molecules for the construction of chemical libraries with new biological activities. The concept of the derivatization of natural products to widen the diversity of the compounds is natural material-related DOS “NMRDOS”. , The criteria for a compound to be considered important for NMRDOS are listed below: (1) to be contained in more than 1 wt % of the total dry weight of the natural materials; (2) easy to be isolated and purified; (3) to have more than three reactive centers in its molecular structure; (4) to have reactive olefin(s); and (5) to show high reactivity for intramolecular reactions, that is, it should be a cyclic molecule. In order to explore the utility of this strategy, we have focused on a monocyclic sesquiterpene zerumbone ( 1 ), found as the major component of the essential oil of wild ginger, Zingiber zerumbet Smith, because it has a powerful latent reactivity, which is derived from three double bonds, two conjugated and one isolated, and a double conjugated carbonyl group in an 11-membered ring structure.…”

Tandem Photoisomerization and Transannular Cyclizations of Zerumbone Epoxide: A Model for Diversity-Oriented Synthesis Using Abundant Natural Products

“…Zerumbone, a cyclic sesquiterpene, is a potential resource available in abundance for natural-materials-related diversity-oriented synthesis . We recently reported synthesizing a 8-oxabicyclo[3.2.1]­octane motif by transannular cyclization of zerumbone, triggered by photoisomerization of the double bonds .…”