Synthesis and Absolute Configuration of Habiterpenol

Abstract

The synthesis of habiterpenol, a G2 checkpoint inhibitor, was achieved through the stereoselective Ti­(III)-mediated radical cyclization of a β-epoxide as the key reaction. Moreover, the absolute configuration of habiterpenol was determined.

Direct dehydroxy(sulfhydryl)xanthylation of alcohols and thiols

“…Xanthates and their analogues 1 have become the focus of research interest due to their widespread applications in a myriad of fields including agrochemicals and pharmaceuticals, 2 organic synthesis 3–7 and materials science. 8 As important functional groups in synthetic chemistry, the extensive employment of alkyl xanthates in the famous Chugaev elimination 3 and Barton–McCombie deoxygenation 4 could generate value-added ( Z )-olefins and alkyl radicals from simple alcohols, 5 having a profound impact on the modification of carbohydrates in organic synthesis. Additionally, expedient access to valuable thiophenols was achieved by the well-known Leuckart thiophenol reaction 6 via nucleophilic xanthylation with diazonium salts.…”

Synthetic exploration of electrophilic xanthylation via powerful N-xanthylphthalimides

“…1A ) 7 at a high temperature, which perhaps serve as key intermediates in the manufacture of viscose from cellulose. 8 Besides, the well-developed Barton–McCombie deoxygenation 9 serving as a convenient source of alkyl radicals from alcohols 10 had a profound impact on the modification of carbohydrates in organic synthesis. Most importantly, organic xanthates could be also utilized as alkyl, acyl or nitrogen radical sources 11 for further diverse or multifunctional transformations.…”

Concise syntheses of (−)-habiterpenol and (+)-2,3-epi-habiterpenol via redox radical cyclization of alkenylsilane

“…6 It contains a phenol moiety in the steroid skeleton with syn -fused CD rings and anti -fused AB and BC rings. We previously achieved the first total synthesis of 1 through Ti( iii )-mediated stereoselective radical cyclization of epoxide 4 , derived from chiral indenyliodide 2 (13 steps from the starting material) and epoxyaldehyde 3 , to construct the cis -fused C ring 7 (Scheme 1A). This enabled the determination of the absolute configuration of 1 and the syntheses of 7- epi - 1 and some habiterpenol analogs for a structure–activity relationship (SAR) study.…”