Synthesis of a Norsesquiterpene Spirolactone/Steroidal Hybrid by Using an Environmentally Friendly Domino Reaction as a Key Step

Abstract

A new class of hybrid molecules is accessed by elaborating testosterone's AB ring into the norsesquiterpene spirolactone AЈBЈ ring. The cyclic ene-acetal 6b, obtained by a PhI-(OAc) 2 -mediated domino process from vicinal unsaturated diol 5, is used for the synthesis of a norsesquiterpene spiro-

Advances in Synthetic Applications of Hypervalent Iodine Compounds

“…[Bis­(acyloxy)­iodo]­arenes-promoted rearrangements have been applied in various ring expansion or ring contraction reactions, − Hofmann rearrangement, − and Claisen rearrangement. − …”

Chemistry of Polyvalent Iodine

“…A DIB-induced domino reaction of the vicinal unsaturated diol 157 afforded cyclic ene-acetal 158 (Scheme 53), which was further utilized in the synthesis of a norsesquiterpene spirolactone/testosterone hybrid 398…”

Access to Diverse Oxygen Heterocycles via Oxidative Rearrangement of Benzylic Tertiary Alcohols

“…In developing such a method, we took inspiration from the Criegee rearrangement of activated alkyl peroxides, wherein the O–O bond is labilized via reaction with an anhydride, promoting C-to-O migration (Scheme A). , We envisioned an analogous transformation in the context of simple alcohols via electrophilic activation with a hypervalent iodine reagent (Scheme B). − Attack of the alcohol on the iodine center would generate an activated intermediate ( 4 ) wherein the oxygen is now electrophilic. This sets the stage for a carbon-to-oxygen alkyl migration, driven by the loss of iodine in its normal valency (IAr), and the resultant oxonium ion ( 5 ) could be trapped by a nucleophile to give the functionalized ether scaffold ( 6 ).…”