84-99-1Relevant articles and documents
Atom economy. Palladium-catalyzed formation of coumarins by addition of phenols and alkynoates via a net C-H insertion
Trost, Barry M.,Toste, F. Dean,Greenman, Kevin
, p. 4518 - 4526 (2007/10/03)
A strategy to achieve ortho substitution of phenols initiated by an ortho-palladation to create coumarins was examined. Indeed, treatment of alkynoates with electron-rich phenols in the presence of a palladium catalyst and an acid does generate coumarins. The scope of the reaction with respect to the phenol and the alkynoates is defined. With unsymmetrical aromatic substrates, generally good regioselectivity that reflects the HOMO coefficients can be observed. In the course of these studies, numerous important naturally occurring coumarins have been synthesized, including fraxinol methyl ether, ayapin, herniarin, xanthoxyletin, and alloxanthoxyletin. The fact that a Pd(0) is the precatalyst rather than a Pd(+2) species and that an acid that reduces Pd(+2) salts, formic acid, functions better than other carboxylic acids raises doubts about the initial working hypothesis. A novel mechanism involving a palladium phenoxide formed from a hydridopalladium carboxylate and phenol is invoked to rationalize the results.
Natural product-like combinatorial libraries based on privileged structures. 1. General principles and solid-phase synthesis of benzopyrans
Nicolaou,Pfefferkorn,Roecker,Cao,Barluenga,Mitchell
, p. 9939 - 9953 (2007/10/03)
Herein we report a novel strategy for the design and construction of natural and natural product-like libraries based on the principle of privileged structures, a term originally introduced to describe structural motifs capable of interacting with a variety of unrelated molecular targets. The identification of such privileged structures in natural products is discussed, and subsequently the 2,2-dimethylbenzopyran moiety is selected as an inaugural template for the construction of natural product-like libraries via this strategy. Initially, a novel solid-phase synthesis of the benzopyran motif is developed employing a unique cycloloading strategy that relies on the use of a new, polystyrene-based selenenyl bromide resin. Once the loading, elaboration, and cleavage of these benzopyrans was established, this new solid-phase method was then thoroughly validated through the construction of six focused combinatorial libraries designed around natural and designed molecules of recent biological interest.
CLAISEN REARRANGEMENTS-XII SYNHESIS OF THE COUMARINS, 5-METHOXYSESELIN, TRACHYPHYLLIN, COUMURRAYIN AND XANTHOXYLETIN
Murray, R. D. H.,Jorge, Z. D.
, p. 3129 - 3132 (2007/10/02)
The structure of the natural coumarins, 5-methoxyseselin 7 and trachyphyllin 14 have been confirmed by total syntheses from 7-acetoxy-5-prenyloxycoumarin 1 in good overall yields.Convenient synthetic routes to the natural coumarins, coumurrayin 4 and xanthoxyletin 10 have also been established.
EFFICIENT SYNTHESES OF THE COUMARINS, COUMURRAYIN, XANTHOXYLETIN AND TRACHYPHYLLIN
Murray, R. D. H.,Jorge, Z. D.
, p. 3403 - 3404 (2007/10/02)
The structure of the natural coumarin, trachyphyllin (12) has been confirmed by a total synthesis from 5,7-diacetoxycoumarin (1).Convenient synthetic routes to coumurrayin (5) and xanthoxyletin (10) have been established.
Synthesis of Linear Pyranocoumarins: Xanthoxyletin, 4-Methylxanthyletin, and 4-Phenylxanthyletin
Ahluwalia, Vindo Kumar,Bhat, Krishna,Prakash, Chandra,Bala, Shashi
, p. 1070 - 1072 (2007/10/02)
A convenient synthesis of linear pyranocoumarins (2H,8H-benzodipyran-2-ones), viz., xanthoxyletin, 4-methylxanthyletin and 4-phenylxanthyletin is described which uses blocking the 8-position of appropriate 7-hydroxycoumarin derivatives with iodine and 1,1-dimethyl-2-propynylation followed by cyclisation.