Stereoselective Synthesis of Polypropionate Units and Heterocyclic Compounds by Cyclopropylcarbinol Ring-Opening with Mercury(II) Salts

Abstract

The mercury(II)-mediated electrophilic ring-opening reaction of various cyclopropylcarbinol derivatives bearing adjacent stereocenters and a remote nucleophilic functional group provides a useful strategy for synthesizing compounds bearing several contiguous stereocenters. These highly diastereoselective reactions occur with anchimeric assistance by the internal nucleophilic moiety and afford synthetically valuable building blocks such as polypropionate units or heterocyclic compounds. The application of cyclopropylcarbinol ring-opening for the preparation of functionalized oxygen heterocycles in natural product synthesis is also outlined.

Formation of Seven‐Membered Carbocycles by the Use of Cyclopropyl Silyl Ethers as Homoenols

“…Regioselectivity was also examined: it is the less‐substituted CC bond of the three‐membered ring that reacts with the oxocarbenium ion (entries 6–8) 12. It is interesting to note that the major products 4 h and 4 i , obtained from 3 h 13a and 3 i ,13b are diastereomeric (Table 1).…”

Creating Stereocenters within Acyclic Systems by C–C Bond Cleavage of Cyclopropanes

“…The combination of this transformation with the enantioselective Simmons–Smith cyclopropanation reaction of allylic alcohols and diastereoselective hydroboration/oxidation allowed access to various polypropionate derivatives 121 (Scheme ). , A useful feature of this transformation is the unique stereodivergence, opening a door for the synthesis of all stereoisomers of a given polypropionate unit. , It was later demonstrated that this reaction could be exploited for the synthesis of the naturally occurring ionophore zincophorin, where the key fragment was synthesized through an intramolecular oxymercuration ring opening of a cyclopropyl carbinol (Scheme ).…”

Active components in leaves of Rhus chinensis Mill.

“…The 3-Methyl-phenol is mainly used in pesticides, medicine, perfume, resin plasticizer, film, antioxidant, and reagents [29][30][31]. Cyclopropyl carbinol is an intermediate used in chemical laboratory research and development of organic compounds and pharmaceuticals [32][33][34].…”