66333-29-7Relevant academic research and scientific papers
A Unified Approach for the Assembly of Atisine- and Hetidine-type Diterpenoid Alkaloids: Total Syntheses of Azitine and the Proposed Structure of Navirine C
Liu, Jie,Ma, Dawei
supporting information, p. 6676 - 6680 (2018/05/03)
A tetracyclic dinitrile was synthesized in twelve steps from cyclohex-2-en-1-one by using a chelation-triggered conjugate addition to a γ-hydroxy-substituted α,β-unsaturated nitrile and an oxidative dearomatization/Diels–Alder cycloaddition cascade as the key steps. The first total synthesis of azitine (in 17 steps) was achieved through a simple reductive cyclization of this intermediate and subsequent transformations while the total synthesis of the proposed structure of navirine C (in 19 steps) was accomplished by a hydrogen-atom-transfer reaction of the tetracyclic dinitrile, Pd/C-catalyzed reductive cyclization, and subsequent functional group manipulation.
Generation of anti-trypanosomal agents through concise synthesis and structural diversification of sesquiterpene analogues
Oguri, Hiroki,Hiruma, Takahisa,Yamagishi, Yutaka,Oikawa, Hideaki,Ishiyama, Aki,Otoguro, Kazuhiko,Yamada, Haruki,Omuraz, Satoshi
supporting information; experimental part, p. 7096 - 7105 (2011/06/22)
To access high-quality small-molecule libraries to screen lead candidates for neglected diseases exemplified by human African trypanosomiasis, we sought to develop a synthetic process that would produce collections of cyclic scaffolds relevant to an assortment of natural products exhibiting desirable biological activities. By extracting the common structural features among several sesquiterpenes, including artemisinin, anthecularin, and transtaganolides, we designed six types of scaffolds with systematic structural variations consisting of three types of stereochemical relationships on the sp3 ring-junctions and two distinct arrays of tricyclic frameworks. A modular and stereodivergent assembly of dienynes exploiting a versatile manifold produced a series of cyclization precursors. Divergent cyclizations of the dienynes employing tandem ring-closing metathesis reactions overrode variant reactivities of the cyclization precursors, leading to the six canonical sets of the tricyclic scaffolds incorporating a diene group. Screenings of trypanosomal activities of the canonical sets, as well as regio- and stereoisomers of the tricyclic dienes, allowed generation of several antitrypanosomal agents defining the three-dimensional shape of the pharmacophore. The candidate tricyclic dienes were selected by primary screenings and further subjected to installation of a peroxide bridge, which generated artemisinin analogues that exhibited potent in vitro anti-trypanosomal activities comparable or even superior to those of artemisinin and the approved drugs, suramin and eflornithine.
Skeletal and stereochemical diversification of tricyclic frameworks inspired by Ca2+-ATPaSe inhibitors, artemisinin and transtaganolide D
Oguri, Hiroki,Yamagishi, Yutaka,Hiruma, Takahisa,Oikawa, Hideaki
supporting information; experimental part, p. 601 - 604 (2009/09/25)
(Chemical Equation Presented) Inspired by the common skeletal motifs of Ca2+-ATPases inhibitors involving artemisinin and transtaganolide D, small molecule collections with the three-dimensional structural diversity of tricyclic systems were designed and expeditiously synthesized (4-5 steps). A synthetic strategy featuring stereochemical diversification of ring-junctions and control of cyclizatlon modes was devised to access varied molecular architectures in a systematic fashion.
ALLYLIC REARRANGEMENT OF CYANOPHOSPHATE. II. SYNTHESIS OF β-CYANO-α,β-UNSATURATED KETONES
Kurihara, Takushi,Miki, Masuo,Yoneda, Ryuji,Harusawa, Shinya
, p. 2747 - 2753 (2007/10/02)
Boron trifluoride-catalyzed allylic rearrangement of the cyanophosphates of α,β-unsaturated ketones (1a-d, 7 and 14) was found to give the allylic phosphates (3a-d, 9 and 16), which were successfully converted to β-cyano-α,β-unsaturated ketones (6a-d, 13 and 20) by acid hydrolysis (0.5 N HCl) followed by manganese dioxide oxidation of the resulting allylic alcohols(5a-d, 11, 12 and 17).The stereochemical features of the allylic phosphates (9 and 16) are discussed.Keywords-α,β-unsaturated ketone; diethyl phosphorocyanidate; cyanophosphate; allylic rearrangement; boron trifluoride etherate; manganese dioxide; β-cyano-α,β-unsaturated ketone
