70946-15-5Relevant academic research and scientific papers
Synthetic Studies of the Rubellin Natural Products: Development of a Stereoselective Strategy and Total Synthesis of (+)-Rubellin C
Gartman, Jackson A.,Tambar, Uttam K.
, p. 11237 - 11262 (2021/08/16)
This manuscript describes our studies of the class of natural products known as the rubellins, culminating in the total synthesis of (+)-rubellin C. These anthraquinone-based natural products contain a variety of stereochemical and architectural motifs, including a 6-5-6-fused ring system, 5 stereogenic centers, and a central quaternary center. Herein, we report our development of a strategy to target the stereochemically dense core and anthraquinone nucleus, including approaches such as a bifunctional allylboron and vinyl triflate reagent, an anthraquinone benzylic metalation strategy, and a late-stage anthraquinone introduction strategy. Our studies culminate in a successful route to highly functionalized anthraquinone-based natural product scaffolds and a stereoselective total synthesis of (+)-rubellin C. These strategies and outcomes will aid in synthetic planning toward anthraquinone-based natural products of high interest.
Total Synthesis of (+)-Rubellin C
Gartman, Jackson A.,Tambar, Uttam K.
supporting information, p. 9145 - 9150 (2020/08/24)
The rubellins are a family of stereochemically complex anthraquinoid heterodimers containing an unprecedented chemical scaffold. Although the rubellins have been known for over three decades, no total synthesis has been achieved since their discovery. The
Total synthesis of isoquinocyclinone
Dischmann, Mike,Frassetto, Timo,Breuning, M. André,Koert, Ulrich
supporting information, p. 11300 - 11302 (2014/10/15)
The total synthesis of the heptacyclic natural product isoquinocyclinone has been achieved. A Hauser annulation was used to assemble the anthraquinone core structure. The unique 2,4,5,6-tetrahydropyrrolo[2,3-b]pyrrole substructure was prepared by alkyne addition to a lactone intermediate and subsequent Ni 0-mediated cyanide addition, the conversion of an O,O- into an N,O-acetal, and final intramolecular N-alkylation. Hauser annulation: An efficient total synthesis of isoquinocyclinone was achieved using a pentacyclic lactone as the key intermediate (see scheme). The pyrrolo-pyrrole substructure was elaborated by acetylide acylation, conversion of an O,O-acetal into an N,O-acetal, and intramolecular amidine alkylation.
Regiocontrolled rearrangement of isobenzofurans
Egan, Ben A.,Paradowski, Michael,Thomas, Lynne H.,Marquez, Rodolfo
experimental part, p. 2086 - 2089 (2011/06/25)
Regioselective alkylation and oxidative rearrangement of isobenzofurans has been achieved to generate substituted 4,8- ihydroxyisochromanones in good yields and with complete regiocontrol.
Rational design of inhibitors of VirA-VirG two-component signal transduction
Maresh, Justin,Zhang, Jin,Tzeng, Yih-Ling,Goodman, Nora A.,Lynn, David G.
, p. 3281 - 3286 (2008/02/08)
VirA-VirG two-component system regulates the vir (virulence) operon in response to specific host factors (xenognosins) in the plant pathogen Agrobacterium tumefaciens. Using whole cell assays, stable inhibitors inspired by the labile natural benzoxazinone inhibitor HDMBOA are developed. It is found that aromatic aldehydes represent a minimal structural unit for activity. In particular, 3-hydroxy-4,6-dimethoxy-3H-isobenzofuran-1-one (HDI) was found to have the highest activity, making it the most potent developed inhibitor of virulence gene expression in Agrobacterium.
Synthesis of arylspiroketals related to the papulacandins via generation of phthalide oxycarbenium ions
Brimble, Margaret A.,Caprio, Vittorio,Johnston, Andrew D.,Sidford, Matthew
, p. 855 - 862 (2007/10/03)
The nucleophilic addition of allylstannanes to oxycarbenium ions generated from phthalide acetate has been studied. The optimum conditions involve the use of trimethylsilyl trifluoromethanesulfonate in dichloromethane at -78 °C. Hydroboration of the allylated products followed by oxidative cyclization provides an efficient synthesis of arylspiroketals which are closely related to the papulacandins.
A regioselective synthesis of dimethyl phthalide-3-phosphonates
Watanabe,Ijichi,Furukawa
, p. 94 - 98 (2007/10/02)
Dimethyl phthalide-3-phosphonates having various substituents on the benzene ring were regioselectively synthesized by the reaction of N,N-diethyl-2-formylbenzamides with tert-butyldimethylsilyl dimethyl phosphite followed by treatment with methanesulfonic acid. N,N-Diethyl-2-formylbenzamides were regioselectively prepared by ortho lithiation-formylation of the corresponding benzamides.
Directed ortho metalation of n,n-diethyl benzamides. Methodology and regiospecific synthesis of useful contiguously tri- and tetra-substituted oxygenated aromatics, phthalides and phthalic anhydrides
De Silva,Reed,Billedeau,Wang,Norris,Snieckus
, p. 4863 - 4878 (2007/10/02)
Full experimental details for the directed ortho metalation approch to a variety of simple ortho-substituted N,N-diethyl benzamides (Table 1) and contiguously 1,2,3- and 1,2,3,4-substituted benzamides (Tables 2) are given. The efficient conversion of these benzamides (6, 10, 12, 13, 18, 19) into phthalides (9a-b, 16b-c, 17) and phthalic anhydrides (8,16a), compounds previously available by demanding, classical methods, is detailed. A short synthesis of iso-ochracinic acid (27) is described.
SYNTHESIS OF THE C-GLYCOSIDE FRAGMENT OF NOGALAMYCIN AND SOME NOGALAMYCIN PRECURSORS
Bates, Mark A.,Sammes, Peter G.,Thomson, Gordon A.
, p. 3037 - 3046 (2007/10/02)
A short, stereoselective method for generation of the fused C-glycoside unit of the anticancer agent nogalamycin is described; in particular, synthesis of the D,E,F ring system.The method utilises a total synthesis of the glycosidic unit from an aryl fury
Synthesis of Functionalized Hydroxyphthalides and Their Conversion to 3-Cyano-1(3H)-isobenzofuranones. The Diels-Alder Reaction of Methyl 4,4-Diethoxybutynoate and Cyclohexadienes
Freskos, John N.,Morrow, Gary W.,Swenton, John S.
, p. 805 - 810 (2007/10/02)
Several methods have been used in the preparation of functionalized hydroxyphthalides.Metalation of N,N-diethyl-3-methoxybenzamide, followed by reaction with dimethylformamide and hydrolysis, furnished 3-hydroxy-4-methoxy-1(3H)-isobenzofuranone in 52perce
