111966-93-9Relevant academic research and scientific papers
A Modular, Enantioselective Synthesis of Resolvins D3, E1, and Hybrids
Anderson, Edward A.,Elbert, bryony L.,Llaveria, Josep,Streatfeild, penelope E.,Urbitsch, Felix
, (2020)
Resolvins D3 and E1 are important signaling molecules in the resolution of inflammation. Here, we report a convergent and flexible strategy to prepare these natural products using Hiyama-Denmark coupling of five- and six-membered cyclic alkenylsiloxanes to connect three resolvin fragments, and control the stereochemistry of the natural product (Z)-alkenes. The modular nature of this approach enables the synthesis of novel resolvin hybrids, opening up opportunities for more-extensive investigations of resolvin biology.
Synthesis of Cyclic Alkenyl Dimethylsiloxanes from Alkynyl Benzyldimethylsilanes and Application in Polyene Synthesis
Gudmundsson, Haraldur G.,Kuper, Christian J.,Cornut, Damien,Urbitsch, Felix,Elbert, Bryony L.,Anderson, Edward A.
, (2019/11/14)
Cyclic dimethylalkenylsiloxanes, useful motifs for (Z)-selective Hiyama cross-coupling, are accessed from alkynyl benzyldimethylsilanes featuring adjacent allylic or homoallylic oxygen substituents by semihydrogenation/debenzylation/cyclization. While formation of 5- and 6-membered rings can be achieved from the free alcohols using fluoride or silanolate, allylic acetate precursors to 5-membered rings display distinct modes of activation. The utility of these compounds is demonstrated through the preparation of a variety of (Z)-alkene-containing polyenes and application to a concise total synthesis of leukotriene B3.
Geometric E→Z Isomerisation of Alkenyl Silanes by Selective Energy Transfer Catalysis: Stereodivergent Synthesis of Triarylethylenes via a Formal anti-Metallometallation
Fa?bender, Svenja I.,Molloy, John J.,Mück-Lichtenfeld, Christian,Gilmour, Ryan
supporting information, p. 18619 - 18626 (2019/11/16)
An efficient geometrical E→Z isomerisation of alkenyl silanes is disclosed via selective energy transfer using an inexpensive organic sensitiser. Characterised by operational simplicity, short reaction times (2 h), and broad substrate tolerance, the reaction displays high selectivity for trisubstituted systems (Z/E up to 95:5). In contrast to thermal activation, directionality results from deconjugation of the π-system in the Z-isomer due to A1,3-strain thereby inhibiting re-activation. The structural importance of the β-substituent logically prompted an investigation of mixed bis-nucleophiles (Si, Sn, B). These versatile linchpins also undergo facile isomerisation, thereby enabling a formal anti-metallometallation. Mechanistic interrogation, supported by a theoretical investigation, is disclosed together with application of the products to the stereospecific synthesis of biologically relevant target structures.
Synthesis of Cyclic Alkenyl Dimethylsiloxanes from Alkynyl Benzyldimethylsilanes and Application in Polyene Synthesis
Gudmundsson, Haraldur G.,Kuper, Christian J.,Cornut, Damien,Urbitsch, Felix,Elbert, Bryony L.,Anderson, Edward A.
, p. 14868 - 14882 (2019/12/02)
Cyclic dimethylalkenylsiloxanes, useful motifs for (Z)-selective Hiyama cross-coupling, are accessed from alkynyl benzyldimethylsilanes featuring adjacent allylic or homoallylic oxygen substituents by semihydrogenation/debenzylation/cyclization. While formation of 5- and 6-membered rings can be achieved from the free alcohols using fluoride or silanolate, allylic acetate precursors to 5-membered rings display distinct modes of activation. The utility of these compounds is demonstrated through the preparation of a variety of (Z)-alkene-containing polyenes and application to a concise total synthesis of leukotriene B3
C- and Si-substituted benzyl(ethynyl)silanes
Zhilitskaya,Yarosh,Yarosh,Voronkov
, p. 69 - 72 (2008/09/18)
Hitherto unknown mono-, di, and triethynyl C- and Si-substituted benzylsilanes were synthesized by the reaction of benzylmagnesium halides with dialkyl(ethynyl)fluorosilanes and of benzyldichloro(hydrocarbyl) silane and benzyltrichlorosilane with ethynylm
Dinuclear asymmetric Zn aldol additions: Formal asymmetric synthesis of fostriecin
Trost, Barry M.,Frederiksen, Mathias U.,Papillon, Julien P. N.,Harrington, Paul E.,Shin, Seunghoon,Shireman, Brock T.
, p. 3666 - 3667 (2007/10/03)
Direct asymmetric aldol reactions constitute a powerful methodology for the efficient synthesis of complex natural products. Herein we report the first application of our recently reported dinuclear Zn-catalyzed direct aldol addition of alkynyl ketones to
Sequential cross-coupling of 1,4-bissilylbutadienes: Synthesis of unsymmetrical 1,4-disubstituted 1,3-butadienes
Denmark, Scott E.,Tymonko, Steven A.
, p. 8004 - 8005 (2007/10/03)
A mild and general and stereospecific cross-coupling reaction of unsymmetrical 1,4-bissilyl-1,3-butadienes has been accomplished. By the use of either a benzyldimethylsilyl or 2-thienyldimethylsilyl unit at one end of the dienylsilanol, a selective cross-
Alkynyliodonium salts in organic synthesis. Development of a unified strategy for the syntheses of (-)-agelastatin A and (-)-agelastatin B
Feldman, Ken S.,Saunders, Joe C.,Wrobleski, Michelle Laci
, p. 7096 - 7109 (2007/10/03)
The total syntheses of natural agelastatin A and agelastatin B were accomplished via a strategy that utilized an alkynyliodonium salt → alkylidenecarbene → cyclopentene transformation to convert a relatively simple amino alcohol derivative to the functionalized core of the agelastatin system. Subsequent manipulations delivered debromoagelastatin, which served as a precursor to both agelastatin A and agelastatin B. Alkylidenecarbene insertion chemoselectivity issues were explored en route to the final targets.
