2008
DOI: 10.1021/ja804738b
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Pd-Catalyzed Enantioselective Aerobic Oxidation of Secondary Alcohols: Applications to the Total Synthesis of Alkaloids

Abstract: Enantioselective syntheses of the alkaloids (−)-aurantioclavine, (+)-amurensinine, (−)-lobeline, and (−)-and (+)-sedamine are described. The syntheses demonstrate the effectiveness of the Pd-catalyzed asymmetric oxidation of secondary alcohols in diverse contexts and the ability of this methodology to set the absolute configuration of multiple stereocenters in a single operation. The utility of an aryne C-C insertion reaction in accessing complex polycyclic frameworks is also described.

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Cited by 153 publications
(75 citation statements)
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References 105 publications
(45 reference statements)
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“…Aurantioclavine (1), [1] clavicipitic acid (2), [2] and hyrtiazepine (3) [3] ( Figure 1) are members of a unique class of indole alkaloids characterized by a novel azepino [5,4,3-cd]-indole ring system. (-)-Aurantioclavine (1) was first isolated in 1981 from Penicillium aurantiovirens, [1] and the absolute configuration was confirmed to be (R) in 2008.…”
Section: Introductionmentioning
confidence: 99%
“…Aurantioclavine (1), [1] clavicipitic acid (2), [2] and hyrtiazepine (3) [3] ( Figure 1) are members of a unique class of indole alkaloids characterized by a novel azepino [5,4,3-cd]-indole ring system. (-)-Aurantioclavine (1) was first isolated in 1981 from Penicillium aurantiovirens, [1] and the absolute configuration was confirmed to be (R) in 2008.…”
Section: Introductionmentioning
confidence: 99%
“…[17] Compound 2u, the identity of which was confirmed by X-ray crystallographic analysis, [18] is the core structural unit of aurantioclavine (3) and other related natural products. [19] Ther eductive cyclization of b,b-disubstituted o-nitrostyrenes was next investigated as this could provide not only an entry to 2,3-disubstituted indoles,b ut also provide us with useful mechanistic information. Gratefully,t reatment of 1v under standard conditions afforded 2-methyl-3-phenylindole (2v)b yadomino sequence involving reductive cyclization and migration of the phenyl group (Scheme 4).…”
Section: Methodsmentioning
confidence: 99%
“…In 2011, Urgoitia et al used two palladacycles in the presence of molecular oxygen in PEG-400, a sustainable reaction media [15]. With a different substrate, diketone product could be obtained also when either MnO2 or Pd(OAc)2 was employed as the oxidant [16]. In a different way, 4,7-di-tertbutyl-acenaphthen-1-ol was oxidized to diketone in the presence of SeO2 (13.5 equiv.)…”
Section: Chemistrymentioning
confidence: 99%
“…Formation of the bromide derivative combining triphenyl phosphine and carbon tetrabromide with 2, followed by an elimination step using DBU at room temperature afforded 4a-4e in good yields. The assignment of E stereochemistry for all styryl compounds was based on the J CH=CH coupling constant of [16][17] …”
Section: Chemistrymentioning
confidence: 99%