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Relevant academic research and scientific papers

First example of molecular iodine-catalyzed allylation and alkynylation of cyclic allylic acetates

Cyclic allylic acetates undergo smooth allylation and alkynylation with allyltrimethylsilane and alkynyl silanes in the presence of molecular iodine under mild conditions to afford the corresponding allylated and alkynylated cyclohexene derivatives in goo

Silver Salt-Mediated Allylation Reactions Using Allyl Bromides

A facile, efficient, and chemoselective synthesis of allylic amides has been developed. Allyl bromides were used as the precursors activated by silver triflate. A Ritter-type reaction readily proceeded to give various allyl amides under mild conditions. The reaction protocol was also applicable to different nucleophilic partners to give a wide range of allyl-substituted products in the absence of a base.

Allylic C-H Alkynylation via Copper-Photocatalyzed Cross-Dehydrogenative Coupling

An efficient, novel photocatalyzed allylic-alkynylation methodology via copper-based cross-dehydrogenative coupling (CDC) is described. Different types of 1,4-enyne compounds were synthesized in one step at room temperature using copper(I) terpyridyl comp

(Guanidine)copper Complex-Catalyzed Enantioselective Dynamic Kinetic Allylic Alkynylation under Biphasic Condition

Highly enantioselective allylic alkynylation of racemic bromides under biphasic condition is furnished in this report. This approach employs functionalized terminal alkynes as pro-nucleophiles and provides 6- and 7-membered cyclic 1,4-enynes with high yields and excellent enantioselectivities (up to 96% ee) under mild conditions. Enantioretentive derivatizations highlight the synthetic utility of this transformation. Cold-spray ionization mass spectrometry (CSI-MS) and X-ray crystallography were used to identify some catalytic intermediates, which include guanidinium cuprate ion pairs and a copper-alkynide complex. A linear correlation between the enantiopurity of the catalyst and reaction product indicates the presence of a copper complex bearing a single guanidine ligand at the enantio-determining step. Further experimental and computational studies supported that the alkynylation of allylic bromide underwent an anti-SN2′ pathway catalyzed by nucleophilic cuprate species. Moreover, metal-assisted racemization of allylic bromide allowed the reaction to proceed in a dynamic kinetic fashion to afford the major enantiomer in high yield.

Copper-Catalyzed Allylic C?H Alkynylation by Cross-Dehydrogenative Coupling

C?H bond functionalization is a well-developed concept that has been thoroughly studied and gives entry to rather complex molecules without the need for previous derivatization of the substrates. The use of copper complexes in allylic C?H bond functionalization under oxidative conditions as an alternative to the well-established palladium-based methodologies remains largely underdeveloped. Here, we show for the first time a selective cross-dehydrogenative coupling reaction between underivatized allylic substrates and terminal alkynes to produce 1,4-enynes in high yields in a single step, using an in situ synthesized copper catalyst and an oxidant.

Chemo- and regioselective reductive deoxygenation of 1-en-4-yn-ols into 1,4-enynes through FeF3 and TfOH co-catalysis

We report chemo- and regioselective direct reductive deoxygenation of 1-en-4-yn-3-ols into 1,4-enynes through FeF3 and TfOH cooperative catalysis under NBSH-mediated conditions. Further, we show the efficient synthesis of a pharmaceutically significant 1,4-enyne. The present methodology can also be used for chemo- and regioselective direct deoxygenation of other alcohols.

Indium(III) catalyzed direct sp3-sp C-C bond formation from alcohols and terminal alkynes

A simple and efficient indium(III)-catalyzed sp3-sp C-C bond formation reaction via direct coupling of alcohols with terminal alkynes has been developed under mild conditions without any ligand, base or additive, in which both of aromatic and aliphatic alkynes and various alcohols such as benzylic, allylic and propargylic alcohols can be tolerated. This simple reaction system provides an attractive approach to a large number of internal alkynes in moderate to good yields, and only generates H2O as the side product.

Copper-catalyzed γ-selective and stereospecific direct allylic alkylation of terminal alkynes: Synthesis of skipped enynes

Skipping out: The title reaction using internal secondary allylic phosphates proceeded with excellent γ regioselectivity and E stereoselectivity to give skipped enynes. Enantioenriched secondary allylic phosphates proceeded with 1,3-anti stereochemistry t

Copper catalyzed regioselective coupling of allylic halides and alkynes promoted by weak inorganic bases

Allylic halides and terminal alkynes couple under CuI catalysis in DMSO or DMF solution. In most cases, sodium carbonate or bicarbonate is sufficient to promote the reaction; less reactive alkynes require catalytic amounts of DBU. Bifunctional alkynes and halides can be reacted selectively according to the stoichiometry used. Trimethylsilyl, hydroxyl, ester and halide groups are tolerated in the alkyne. Most halides react without allylic rearrangement. The method is suitable for the synthesis of functionalized enynes.

Catalytic decarboxylative sp-sp3 coupling

A palladium-catalyzed 1,4-enyne synthesis was developed based the decarboxylative coupling of acetylides with allyl electrophiles. Stereochemical studies have implicated palladium-allyl-acetylides as intermediates. Thus, decarboxylative metalation was established as an environmentally benign alternative to transmetalation from alkynyl tin reagents. Copyright