160309-18-2Relevant academic research and scientific papers
Preparation and conversion of chiral O-isopropylidene-protected 4-aminocyclohexenol to various key intermediates toward narcissus alkaloids
Elango, Shanmugham,Wang, Ying-Chuan,Cheng, Chien-Liang,Yan, Tu-Hsin
, p. 3757 - 3759 (2002)
Enantiomerically pure 4-amino-5,6-O-isopropylidenedioxycyclohex-2-en-1-ol, conveniently prepared by the union of O-isopropylidenedioxycyclohexadiene with camphor-based chloronitroso ester, was employed in the synthesis of versatile key intermediates toward narcissus alkaloids.
Chemoenzymatic synthesis of amaryllidaceae constituents and biological evaluation of their C-1 analogues. the next generation synthesis of 7-deoxypancratistatin and trans -dihydrolycoricidine
Collins, Jonathan,Rinner, Uwe,Moser, Michael,Hudlicky, Tomas,Ghiviriga, Ion,Romero, Anntherese E.,Kornienko, Alexander,Ma, Dennis,Griffin, Carly,Pandey, Siyaram
scheme or table, p. 3069 - 3084 (2010/07/17)
An efficient synthesis of C-1 derivatives of 7-deoxypancratistatin is reported. The key steps include the following: selective opening of an epoxide with aluminum acetylide in the presence of an aziridine; solid-state silica-gel-catalyzed opening of an aziridine; and oxidative cleavage of a phenanthrene core and its recyclization to phenanthridone to provide the key C-1 aldehyde 22. The conversion of this aldehyde to C-1 acetoxymethyl and C-1 hydroxymethyl derivatives is described along with the evaluation of their biological activity against several cancer cell lines and in an apoptosis study. The C-1 acetoxymethyl derivative has shown promising activity comparable to that of the natural product. In addition, a total synthesis of trans-dihydrolycoricidine and a formal total synthesis of 7-deoxypancratistatin are reported from aldehyde 22. Detailed experimental and spectral data are provided for all new compounds.
Cyclotrimerization approach to unnatural structural modifications of pancratistatin and other amaryllidaceae constituents - Synthesis and biological evaluation
Hudlicky, Tomas,Moser, Michael,Banfield, Scott C.,Rinner, Uwe,Chapuis, Jean-Charles,Pettit, George R.
, p. 1313 - 1337 (2007/10/03)
The phenanthridone core of pancratistatin lacking all aromatic oxygenation was prepared by cyclotrimerization of acetylene-containing scaffolds 30 and 41, reflecting the natural and the C-1 epi configuration, respectively, of the amino inositol moiety. Th
Total synthesis and biological evaluation of Amaryllidaceae alkaloids: narciclasine, ent-7-deoxypancratistatin, regioisomer of 7-deoxypancratistatin, 10b-epi-deoxypancratistatin, and truncated derivatives.
Hudlicky, Tomas,Rinner, Uwe,Gonzalez, David,Akgun, Hulya,Schilling, Stefan,Siengalewicz, Peter,Martinot, Theodore A,Pettit, George R
, p. 8726 - 8743 (2007/10/03)
Biocatalytic approaches have yielded efficient total syntheses of the major Amaryllidaceae alkaloids, all based on the key enzymatic dioxygenation of suitable aromatic precursors. This paper discusses the logic of general synthetic design for lycoricidine, narciclasine, pancratistatin, and 7-deoxypancratistatin. Experimental details are provided for the recently accomplished syntheses of narciclasine, ent-7-deoxypancratistatin, and 10b-epi-deoxypancratistatin via a new and selective opening of a cyclic sulfate over aziridines followed by aza-Payne rearrangement. The structural core of 7-deoxypancratistatin has also been degraded to a series of intermediates in which the amino inositol unit is cleaved and deoxygenated in a homologous fashion. These truncated derivatives and the compounds from the synthesis of the unnatural derivatives have been tested against six important human cancer cell lines in an effort to further develop the understanding of the mode of action for the most active congener in this group, pancratistatin. The results of the biological activity testing as well as experimental, spectral, and analytical data are provided in this manuscript for all relevant compounds.
Structure assignment of aminoconduritols by 15N NMR correlation spectroscopy; synthesis of a positional isomer of 7-deoxypancratistatin
Schilling, Stefan,Rinner, Uwe,Chan, Collin,Ghiviriga, Ion,Hudlicky, Tomas
, p. 1659 - 1667 (2007/10/03)
A positional isomer of 7-deoxypancratistatin was synthesized in 12 steps from epoxyaziridines 4 and 5. An intermolecular opening of the aziridine rather than the epoxide in the early stages of the synthesis led to 13, which did not match the properties of
Use of Electrochemical Methods as an Alternative to Tin Reagents for the Reduction of Vinyl Halides in Inositol Synthons
Hudlicky, Tomas,Claeboe, Christopher D.,Brammer Jr., Larry E.,Koroniak, Lukasz,Butora, Gabor,Ghiviriga, Ion
, p. 4909 - 4913 (2007/10/03)
Several vinyl halides previously used in inositol syntheses were subjected to electrochemical reduction. The unreactivity of allylic alcohols or allylic ethers at the applied potentials allowed the selective reduction of vinyl halides to olefins. Electrochemical methods provide for selective reduction of vinyl iodides over vinyl bromides, with better yields than analogous tin methodology. Cinnamyl ethers were reductively cleaved at -3.2 V (vs Ag/AgNO3) in the presence of alkyl allyl ethers to provide selective deprotection. The electrochemical reduction of vinyl halides in the presence of a vinyloxirane or vinylaziridine is accompanied by the solvolysis of the strained rings. Yields and conditions are reported and compared to those from standard tin-induced dehalogenation.
Toluene-dioxygenase-mediated cis-dihydroxylation of aromatics in enantioselective synthesis. Iterative glycoconjugate coupling strategy and combinatorial design for the synthesis of oligomers of nor-saccharides, inositols and pseudosugars with interesting
Hudlicky, Tomas,Abboud, Khalil A.,Entwistle, David A.,Fan, Rulin,Maurya, Rakesh,Thorpe, Andrew J.,Bolonick, Joel,Myers, Brian
, p. 897 - 911 (2007/10/03)
Vinyl epoxides 18 and 31 and vinylaziridines 24 and 25 derived from chloro- or bromocyclohexadiene-cis-diols 9 have been condensed with protected cyclitols 19, 37, and 46 in an iterative manner to generate dimeric, trimeric and tetrameric conduritol or am
Toluene dioxygenase-mediated cis-dihydroxylation of aromatics in enantioselective synthesis. Asymmetric total syntheses of pancratistatin and 7-deoxypancratistatin, promising antitumor agents
Hudlicky, Tomas,Tian, Xinrong,K?nigsberger, Kurt,Maurya, Rakesh,Rouden, Jacques,Fan, Boreas
, p. 10752 - 10765 (2007/10/03)
Whole-cell biooxidation of bromobenzene with Pseudomonas putida 39D or the recombinant Escherichia coli JM109 (pDTG601) yields (1S,2S)-3-bromocyclohexa-3,5-diene-1,2-diol (9a), which is protected as the acetonide and converted to vinylaziridines 7, 15a, 6
Concise syntheses of 1,2-L-chiro-inositol conjugates and oligomers - A novel class of saccharide mimics with promising molecular properties
Hudlicky, Tomas,Abboud, Khalil A.,Bolonick, Joel,Maurya, Rakesh,Stanton, Michelle L.,Thorpe, Andrew J.
, p. 1717 - 1718 (2007/10/03)
Calcium complexes with novel amino-inositol conjugates to form secondary extended helical structures are reported.
