79184-98-8

Upstream product

• 108-94-1 cyclohexanone 
• 4342-22-7 1-(triethylsilyloxy)cyclohexene 
• 994-30-9 triethylsilyl chloride 
• 70156-98-8 6-bromo-1,4-dioxaspiro[4,5]dec-6-ene 
• 79184-88-6 Triethyl-(2-phenylselanyl-cyclohex-1-enyloxy)-silane 

Relevant academic research and scientific papers

One-Pot Synthesis of Silylated Enol Triflates from Silyl Enol Ethers for Cyclohexynes and 1,2-Cyclohexadienes

Regiocontrolled synthesis of precursors for strained cyclohexynes and 1,2-cyclohexadienes is described based on one-pot rearrangement of silyl enol ether followed by formation of enol triflate. Treatment of silyl enol ether with a combination of LDA and tBuOK led to the migration of the silyl group to generate α-silyl enolate, which was treated with Comins' reagent to provide the corresponding enol triflate. The transient α-silylated lithium enolate was smoothly isomerized in the presence of stoichiometric amount of water within one hour at room temperature, providing precursors for cyclohexynes exclusively in one pot. Effects of silyl groups, isomerization of the lithium enolate, and regiocontrolled generation of these precursors for these strained molecules were also investigated.

Nitrone Cycloadditions of 1,2-Cyclohexadiene

We report the first 1,3-dipolar cycloadditions of 1,2-cyclohexadiene, a rarely exploited strained allene. 1,2-Cyclohexadiene is generated in situ under mild conditions and trapped with nitrones to give isoxazolidine products in synthetically useful yields. The reactions occur regioselectively and exhibit a notable endo preference, thus resulting in the controlled formation of two new bonds and two stereogenic centers. DFT calculations of stepwise and concerted reaction pathways are used to rationalize the observed selectivities. Moreover, the strategic manipulation of nitrone cycloadducts demonstrates the utility of this methodology for the assembly of compounds bearing multiple heterocyclic units. These studies showcase the exploitation of a traditionally avoided reactive intermediate in chemical synthesis.

Concise Approach to Cyclohexyne and 1,2-Cyclohexadiene Precursors

Silyl triflate precursors to cyclic alkynes and allenes serve as valuable synthetic building blocks. We report a concise and scalable synthetic approach to prepare the silyl triflate precursors to cyclohexyne and 1,2-cyclohexadiene. The strategy involves a retro-Brook rearrangement of an easily accessible cyclohexanone derivative, followed by triflation protocols. This simple, yet controlled, method should enable the further study of strained alkynes and allenes in chemical synthesis.

Silyl Tosylate Precursors to Cyclohexyne, 1,2-Cyclohexadiene, and 1,2-Cycloheptadiene

Transient strained cyclic intermediates have become valuable intermediates in modern synthetic chemistry. Although silyl triflate precursors to strained intermediates are most often employed, the instability of some silyl triflates warrants the developmen

Practical Synthesis of Precursors of Cyclohexyne and 1,2-Cyclohexadiene

This study investigated a practical method for regiocontrolled synthesis of precursors of strained cyclohexynes and 1,2-cyclohexadienes, which is a one-pot procedure consisting of a rearrangement of silyl enol ether and subsequent formation of the enol triflates. Triethylsilyl enol ether, derived from cyclohexanone, was treated with a combination of LDA and t -BuOK in n -hexane/THF to encourage the migration of the silyl group to generate an α-silyl enolate. Subsequently, the α-silyl enolate was reacted with Comins' reagent to yield the corresponding enol triflate. Finally, the α-silylated trisubstituted lithium enolate for the synthesis of 1,2-cyclohexadiene precursor was isomerized in the presence of a stoichiometric amount of water for one hour at room temperature to exclusively provide tetrasubstituted lithium enolate for the synthesis of cyclohexyne precursor in one pot.

PREPARATION OF α-TRIALKYLSILYL KETONES FROM α-PHENYLSELENO DERIVATIVES VIA THEIR SILYL ENOL ETHERS

On treatment with metallic lithium in the presence of dimethylaminonaphthalene, trialkylsilyl enol ethers of α-phenylseleno ketones were converted into the corresponding α-trialkylsilyl ketones in good yields.