Hypervalent Iodine(III)-induced Intramolecular Cyclization Reaction of Substituted Phenol Ethers with an Alkyl Azido Side-chain: A Novel and Efficient Synthesis of Quinone Imine Derivatives.

Pyrroloiminoquinone Alkaloids: Discorhabdins and Makaluvamines

“…We have developed a facile and direct preparation of the quinone imine derivatives, and very recently communicated the synthesis of pyrroloiminoquinones from the indole bearing an alkyl azido sidechain [21]. The starting substrate was prepared as follows.…”

Development of Novel Reactions Using Hypervalent Iodine(III) Reagents: Total Synthesis of Sulfur-Containing Pyrroloiminoquinone Marine Product, (±)-Makaluvamine F

“…Type II involves the reactions of phenol ethers, wherein the aromatic ring reacts with the hypervalent iodine reagent and generates a cation radical intermediate [ArH + ◊] (equation 4). 16 Very recently, we have reported successful applications of the intramolecular Type II reaction using the activated hypervalent iodine reagents such as PIFA-BF 3 ◊Et 2 O and PIFA-Me 3 SiOTf to obtain biaryl compounds ( equation 5), 19,20 quinone imine derivatives (equation 6), 21,22 and sulfur-containing heterocycles (equation 7). 23 In this paper we report a full account of the total synthesis of potent cytotoxic makaluvamine F (1) using our newly developed hypervalent iodine induced reactions.…”

Seven-Membered Rings through Metal-Free Rearrangement Mediated by Hypervalent Iodine

“…Compounds 5f and 8f could not be separated from each other by chromatography column or HPLC. The proposed mechanism for the formation of 12f was based on desaromatization reactions previously described in literature [47,48] (Scheme 5). The first step is the transformation of 3f into the seven-membered ring compound 5f , as shown in (Scheme 2), followed by the formation of the charge transfer complex 16 from 5f and HTIB.…”