Straightforward Stereoselective Synthesis of Seven-Membered Oxa-Bridged Rings through In Situ Generated Cycloheptenol Derivatives

Abstract

An iodine-mediated stereoselective synthesis of seven-membered oxa-bridged rings via in situ generated cycloheptenols was reported. This process was realized through the combination of C−C σ-bond cleavage and C−O bond-forming reactions in a one-pot fashion from simple and easily accessible raw materials. The formation of carbon radicals initiated by I 2 was the key to the reaction.

Cu-Catalyzed Diarylthiolation of Ynones with Aryl Iodides and Elemental Sulfur: An Access to Tetrasubstituted (Z)-1,2-Bis(arylthio)alkenes and Benzo[b][1,4]dithiines

“…Ynones 1 were prepared according to our pervious report; all ynones 1 are known compounds that are synthesized or used in published methods . Alkyne (6.00 mmol, 1.20 equiv) and anhydrous THF (15 mL) were added to a 50 mL two-neck round-bottom flask.…”

Recent Progress in Cyclic Aryliodonium Chemistry: Syntheses and Applications

“…The construction of strained seven-membered rings containing a bridged biaryl atropisomer is challenging. − Based on the previous achievements in atropisomer construction, a facile approach to construct lactone-bridged biaryl atropisomers 144 from acyoxylated biaryls 143 has been developed . The approach involves a palladium-catalyzed intramolecular diastereoselective Mizoroki–Heck cyclization (Scheme ).…”

Stereoselective synthesis of 1,3,5-trienes from alkynones and allyl carbonyl compounds through C–C σ-bond cleavage under transition-metal-free conditions

“…On the other hand, transition-metal-free C–C σ-bond cleavage reactions of unstrained molecules are highly challenging and important in synthetic organic chemistry, because they can reorganize the molecular skeleton of the starting materials, giving rise to complex target molecules which are difficult to obtain by other methods. 7 Therefore, it is very attractive to apply the transition-metal-free C–C σ-bond cleavage reactions of unstrained molecules to the synthesis of conjugated trienes. Herein, we report a transition-metal-free protocol for the stereocontrolled synthesis of substituted 1,3,5-trienes through the C–C σ-bond cleavage reaction of allyl carbonyl compounds (Scheme 1).…”