123332-18-3Relevant articles and documents
Copper-Catalyzed Enantioselective Domino Arylation/Semipinacol Rearrangement of Allylic Alcohols with Diaryliodonium Salts
Wu, Hua,Wang, Qian,Zhu, Jieping
, p. 13037 - 13041 (2017)
A copper-catalyzed enantioselective arylative semipinacol rearrangement of allylic alcohols was developed. In the presence of a catalytic amount of an in situ generated chiral copper-bisoxazoline complex, reaction of allylic alcohols with diaryliodonium salts afforded spirocycloalkanones in high yields with high diastereo- and enantioselectivities. A two-point binding model engaging the carbon–carbon double bond and the proximal hydroxyl group was proposed to be responsible for the highly efficient chirality transfer.
Catalytic enantioselective Negishi reactions of racemic secondary benzylic halides
Arp, Forrest O.,Fu, Gregory C.
, p. 10482 - 10483 (2005)
This report describes the first enantioselective cross-couplings of racemic secondary benzylic halides, specifically, nickel-catalyzed Negishi reactions of bromides and chlorides. The catalyst components are commercially available and air-stable, and the reaction is not highly oxygen- or moisture-sensitive (it can be set up in the air). The method has been applied to the catalytic enantioselective synthesis of intermediates employed by others in the generation of bioactive compounds (e.g., trikentrin A and an androgen receptor agonist). Copyright
Photochemical generation and reversible cycloaromatization of a nine-membered ring cyclic enediyne
Pandithavidana, Dinesh R.,Poloukhtine, Andrei,Popik, Vladimir V.
experimental part, p. 351 - 356 (2009/06/18)
Irradiation of the nine-membered ring enediyne precursor, which has one of its triple bonds masked as cyclopropenone, efficiently(φ = 0.34) generates the reactive 4,5-benzocyclonona-2,6-diynol. The latter rapidly equilibrates with the corresponding 1,4-didehydronaphthalene diradical and then undergoes rate- limiting hydrogen abstraction to produce the ultimate product of the Bergman cyclization, benz[f]indanol.
Benzindene
Carpino, Louis A.,Lin, Yao-Zhong
, p. 247 - 250 (2007/10/02)
A convenient route to benzindene (1) has been developed in which 2-methylnaphthalene is brominated sequentially in the α-position and the methyl group followed by application of a standard malonic ester route to propionic acid 10.Cyclization of 10 via the acid chloride gave 11 (76percent).Simultaneous reduction of the carbonyl group and hydrogenolysis of the aryl bromide linkage of 11 gave secondary alcohol 12 in 55.4percent yield.Sulfuric acid dehydration of 12 gave 1 (85percent).Less successful routes to 1 involved dithionite reduction of unsaturated sulfones 6.Dihydro derivative 7 could be synthesized in 72percent yield by magnesium/methanol reduction of 5b.
