Synthetic studies directed toward the proposed structure for heteroscyphic acid A

Abstract

A route to the carbon skeleton of the proposed structure for heteroscyphic acid A was developed utilizing a Mn(III)/Cu(II) mediated oxidative free-radical cyclization and nucleophilic addition to (3-methylpentadienyl)iron(1+) cation.

Recent Applications of Acyclic (Diene)iron Complexes and (Dienyl)iron Cations in Organic Synthesis

“…[22] To this end, 5-hexen-1-ol ( 43 ) was transformed into the decahydronaphthalene ester 44 (Scheme 9); the fused bicyclic skeleton was formed by a Mn-mediated oxidative radical cyclization. [23] Generation of the ester enolate anion from 44 and addition to the Fe(CO) 2 PPh 3 ligated pentadienyl cation 45 gave complex 46 .…”

Stereocontrolled Synthesis of Polyfunctionalized cis-Decalins from 2-Methoxyphenols: Total Syntheses of (±)-Eremopetasidione, (±)-3β-Angeloyloxyfuranoeremophilane, and (±)-3β-Methacryloyloxyfuranoeremophilane

“…The structural complexity of the isolated natural products demands the development of new and efficient strategies to construct stereochemically rich and multifunctional decalins. For this reason, there has been a great deal of interest in developing a multitude of methods for their synthesis, as reflected by the flurry of recent reports in this area by various groups. , …”

Reactivity of (3-Methylpentadienyl)iron(1+) Cation: Late-stage Introduction of a (3-Methyl-2Z,4-pentadien-1-yl) Side Chain

“…It should be noted that attempts at reduction of the 5 using H 2 and a poisoned catalyst were unsuccessful. As part of our interest in the application of organoiron complexes to organic synthesis 7 , we have examined the reactivity the (3-methylpentadienyl)Fe(CO) 2 PPh 3 + cation (6, Scheme 2) with nucleophiles as a means for late-stage introduction of the 3-methyl-2Z,4-pentadienyl sidechain 8 . Scheme 1.…”