470671-23-9Relevant articles and documents
Benzannulation of triynes to generate functionalized arenes by spontaneous incorporation of nucleophiles
Karmakar, Rajdip,Yun, Sang Young,Chen, Jiajia,Xia, Yuanzhi,Lee, Daesung
, p. 6582 - 6586 (2015)
The thermal reaction of ester-tethered 1,3,8-triynes provides novel benzannulation products with concomitant incorporation of a nucleophile. Evidence suggests that this reaction proceeds via an allene-enyne intermediate generated by an Alder-ene reaction in the first step. Depending on the substituent of the alkyne moiety on the allene-enyne intermediate, the subsequent transformation can take one of two different paths, each leading to discrete aromatization products. The benzannulation of a silane-substituted 1,3,8-triynes provides arene products with a nucleophile incorporated onto the newly formed benzene core, whereas an aryl substituent leads to nucleophile trapping at the benzylic carbon atom connected to the aryl substituent. The formation of these two different products results from the involvement of two regioisomeric allene-enyne intermediates.
Silver-Catalyzed Annulation of Arynes with Nitriles for Synthesis of Structurally Diverse Quinazolines
Ghorai, Sourav,Lin, Yongjia,Xia, Yuanzhi,Wink, Donald J.,Lee, Daesung
supporting information, p. 626 - 630 (2020/01/31)
An efficient silver catalyzed annulation reaction of aryne with nitriles to generate quinazolines is described. Arynes generated from triynes or tetraynes through a hexadehydro Diels-Alder reaction readily participated in an [A + 2B] mode of annulation with nitriles in the presence of AgSbF6 catalyst. The mechanism was explored by DFT calculations, which supports the silver-catalyzed formation of nitrilium ion as a key intermediate. This annulation generates an array of polysubstituted novel quinazoline derivatives with excellent regioselectivity.
Silver-Catalyzed Selective Multicomponent Coupling Reactions of Arynes with Nitriles and Isonitriles
Ghorai, Sourav,Lin, Yongjia,Xia, Yuanzhi,Wink, Donald J.,Lee, Daesung
supporting information, p. 642 - 647 (2020/01/31)
Pathway selective aryne-based novel multicomponent coupling reactions with isonitriles and nitriles are described. Crucial to these reactions is the formation of a silver-aryne complex, which shows differential reactivity toward isonitriles and nitriles to form two different forms of ortho-nitrilium organosilver arene species. Interception of the nitrilium of an aryne-isonitrile adduct with another isonitrile leads to the formation of benzocyclobutene-1,2-diimines, whereas the nitrilium of an aryne-nitrile adduct renders selective formation of 3H-indol-3-imines or 3-iminoindolin-2-ol depending on the structure of the nitrile employed.
Synthesis of Imides, Imidates, Amidines, and Amides by Intercepting the Aryne-Isocyanide Adduct with Weak Nucleophiles
Ghorai, Sourav,Lee, Daesung
supporting information, p. 7390 - 7393 (2019/10/02)
New aryne-based multicomponent coupling reactions for the formation of functionalized aromatic compounds have been developed. Arynes generated from triynes or tetraynes through the hexadehydro Diels-Alder reaction readily react with isocyanide to generate nitrilium intermediate. Intercepting this nitrilium species with various weak nucleophile including carboxylic acids, alcohols, sulfonamides, or water generated the corresponding imides, imidates, amidines, or amides. The high regioselectivity of these transformations was mainly controlled by the substituents of the arynes.
Hydroarylation of arynes catalyzed by silver for biaryl synthesis
Lee, Nam-Kyu,Yun, Sang Young,Mamidipalli, Phani,Salzman, Ryan M.,Lee, Daesung,Zhou, Tao,Xia, Yuanzhi
supporting information, p. 4363 - 4368 (2014/04/03)
A new biaryl synthesis via silver-catalyzed hydroarylation of arynes from acyclic building blocks with unactivated arenes in intra- and intermolecular manners has been developed. The previously observed Diels-Alder reactions of arynes with arene were not observed under the current silver-catalyzed conditions. Deuterium scrambling and DFT calculations suggest a stepwise electrophilic aromatic substitution mechanism through the formation of a Wheland-type intermediate followed by a water-catalyzed proton transfer in the final step of the hydroarylation.
From highly enantioselective catalytic reaction of 1,3-diynes with aldehydes to facile asymmetric synthesis of polycyclic compounds
Turlington, Mark,Du, Yuhao,Ostrum, Samuel G.,Santosh, Vishaka,Wren, Kathryne,Lin, Tony,Sabat, Michal,Pu, Lin
supporting information; experimental part, p. 11780 - 11794 (2011/09/16)
(S)-1,1′-Binaphth-2-ol (BINOL) in combination with ZnEt2, Ti(OiPr)4, and biscyclohexylamine was found to catalyze the highly enantioselective (83-95% ee) addition of various 1,3-diynes to aldehydes of diverse structures. This method provides a convenient pathway to generate a number of optically active dienediynes as the acyclic precursors to polycyclic compounds. The chiral dienediynes undergo highly chemoselective Pauson-Khand (PK) cycloaddition in benzaldehyde by using [Rh(cod)Cl]2 as the catalyst in the presence of rac-BINAP. High diastereoselectivity (up to >20:1) has also been achieved with the chiral dienediyne substrates containing a bulky substituent adjacent to the chiral center. In the presence of the Grubbs II catalyst, ring-closing enyne metathesis of the PK cycloaddition products led to the formation of the desired 5,5,7- and 5,5,8-fused tricyclic compounds. Further highly diastereoselective Diels-Alder reaction of a 5,5,7-tricyclic compound with maleic anhydride produced a 5,5,7,6-polycyclic product. The asymmetric synthesis of polycyclic compounds from optically active dienediynes has established a novel and efficient synthetic route to the structural framework of many biologically significant molecules.
Selectivity in the Ruthenium-catalyzed Alder ene reactions of di- and triynes
Eun, Jin Cho,Lee, Daesung
, p. 6692 - 6693 (2008/02/04)
Ruthenium-catalyzed Alder ene reactions between diynes and triynes with terminal alkenes gave the corresponding enynes and enediynes with high regio- and site-selectivity. The selectivity profile clearly indicates that one of the alkynyl moieties of 1,3-diynes not participating in the reaction determines the regiochemistry, whereas the interplay between steric hindrance and polar substituents at the propargylic sites determines the site-selectivity. Copyright
Single-crystal-to-single-crystal topochemical polymerizations of a terminal diacetylene: Two remarkable transformations give the same conjugated polymer
Ouyang, Xi,Fowler, Frank W.,Lauher, Joseph W.
, p. 12400 - 12401 (2007/10/03)
Host-guest chemistry was used to prepare a cocrystal of a dipyridyl substituted oxalamide host and a resorcinol derivative of a terminal diacetylene. X-ray crystallography revealed that the molecules assemble into a triple-helix with the diacetylene functionalities aligned in the center of the helix. Upon heating, the diacetylenes polymerize to give the corresponding polymer. In a second experiment, the X-ray structure of the crystalline hydrate of the same diacetylene also showed a suitable alignment of the diacetylene functionalities. These crystals polymerize at only 50 °C with the C1 carbon end of the diacetylene undergoing an unprecedented 2.4 A inward swinging movement. This results in a remarkable 9% increase in crystal density. These are the first structurally characterized polymerizations of any terminal diacetylene. A detailed comparison of the two sets of structural changes offers an interesting insight into the precise trajectories of polymerization reactions. Copyright
Bulky trialkylsilyl acetylenes in the Cadiot-Chodkiewicz cross-coupling reaction
Marino, Joseph P.,Nguyen, Hanh Nho
, p. 6841 - 6844 (2007/10/03)
Bulky trialkylsilyl-protected alkynes such as triethylsilyl (TES), tert-butyldimethylsilyl (TBS), and tri-isopropylsilyl (TIPS) acetylenes underwent the Cadiot-Chodkiewicz cross-coupling reaction with different bromoalkynes to form a variety of synthetically useful unsymmetrical diynes in good yields. The diyne alcohol 10 was transformed regio- and stereoselectively into enynes by hydrotelluration, carbometalation, and reduction reactions.
