183312-34-7

Upstream product

• 917-92-0 3,3-Dimethylbut-1-yne 
• 6630-33-7 ortho-bromobenzaldehyde 
• 210964-22-0 o-(3,3-dimethylbut-1-ynyl)benzyl alcohol 
• 26260-02-6 2-iodobenzaldehyde 
• 5159-41-1 2-iodobenzyl alcohol 

Downstream Products

• 183312-23-4 1-[2-(3,3-Dimethyl-but-1-ynyl)-phenyl]-hept-2-yn-1-ol 
• 220649-66-1 C₂₇H₂₈ 
• 571184-14-0 ethyl 4-[2-(3,3-dimethyl-1-butynyl)phenyl]-4-hydroxy-2-butynoate 
• 955378-75-3 C₁₈H₂₄OSi 
• 1146963-89-4 C₁₇H₂₂ 
• 173414-56-7 2-(3,3-dimethylbut-1-yn-1-yl)benzoic acid 
• 217312-71-5 1-(3,3-dimethylbut-1-yn-1-yl)-2-ethynylbenzene 
• 1378013-24-1 1-(3,3-dimethylbut-1-yn-1-yl)-2-(⁽²⁾H)ethynylbenzene 
• 1613036-47-7 1-(2-(3,3-dimethylbut-1-yn-1-yl)phenyl)-2,2,2-trifluoroethanol 

Relevant academic research and scientific papers

Benzo[b]fluorenes formed in the thermal cyclization of 3-ene-1,6-diynes

A three-step preparation of the benzofluorene core is presented. The last step involves thermal cyclization of 3-ene-1,6-diyne (7) leading to the formation of four benzofluorene derivatives, one of which has been investigated by X-ray analysis. The harsh thermal conditions indicate that the cyclization of 7 might not proceed via a biradical intermediate as would be anticipated by a mechanistic proposal from Ueda.

Light-Enabled Radical 1,4-Aryl Migration Via a Phospho-Smiles Rearrangement

Rearrangement reactions in organic chemistry are attractive strategies to build efficiently complex scaffolds, in just one step, from simple starting materials. Among them, aryl migrations are certainly one of the most useful and straightforward rearrangement for building attractive carbon-carbon bonds. Of note, anionic aryl migration reactions have been largely described compared to their radical counterparts. Recently, visible-light catalysis has proven its efficiency to generate such radical rearrangements due to the concomitant loss of a particle (often CO2 or SO2), which is the driving-force of the reaction. Here, we disclose a Smiles-type rearrangement, triggered by a phosphorus-containing unit (arylphosphoramidate), therefore called "phospho-Smiles"rearrangement, allowing a Csp2-Csp2 bond formation thanks to a 1,4-aryl migration reaction. In addition, combining this approach with a radical hydroamination/amination reaction produces an amination/phospho-Smiles cascade particularly attractive, for instance, to investigate the synthesis of the phthalazine core, a scarcely described scaffold of interest for medicinal chemistry projects.

Construction of dibenzo-fused seven- to nine-membered carbocycles via Bronsted acid-promoted intramolecular Friedel - Crafts-type alkenylation

Bronsted acid-promoted intramolecular hydroarylation of alkynylbenzenes carrying an arylalkyl group at the ortho-position leads to alkylidenedibenzo[a,d]cycloheptenes, -octenes and -nonenes in up to quantitative yield with complete regioselectivity. The scope and limitation of this reaction and application to the synthesis of tricyclic antidepressants are described.

Synthesis of Functionalized 1H-Isochromene Derivatives via a Au-Catalyzed Domino Cycloisomerization/Reduction Approach

A Au-catalyzed versatile and efficient access to 1H-isochromenes is reported. The efficiency of the [AuCl2(Pic)] complex (1-5 mol %) was demonstrated and allowed a domino cycloisomerization/reduction reaction process starting from a wide range of functionalized ortho-alkynylbenzaldehydes and one example of ortho-alkynylpyridinylaldehyde. The smooth reaction conditions were amenable to aryl- and alkyl-substituted alkynyl derivatives, as well as functionalized halogen and ether moieties, leading to a chemo- and regioselective 6-endo-cyclization with good to excellent yields.

Fluoro-ene reaction versus [2+2] cycloaddition in the thermal C 2-C6 cyclization of enyne-allenes: An experimental and theoretical investigation

A series of fluoroalkyl-substituted enyne-allenes have been synthesized by a new route with the aim of elucidating the possibility of a fluoro-ene reaction via an intermediate fulvenyl diradical generated in the thermal C 2-C6 (Schmittel) cyclization reaction. As a result of the strong C-F bond, fluorine atom transfer was not observed. Instead, 1H-cyclobuta[a]indenes were formed in good yields despite the high strain energy. DFT calculations at the B3LYP level of theory indicated that although the fluoro-ene reaction is the most exothermic reaction available, cyclobutene formation is kinetically favored over the [1,5]-fluorine shift by 5-15 kcal mol-1 in various model compounds. Copyright

Silver-catalyzed domino hydroarylation/cycloisomerization reactions of ortho-alkynylbenzaldehydes: An entry to functionalized isochromene derivatives

A Ag-catalyzed versatile and efficient access to 1H,1-arylisochromenes is reported. Starting from ortho-alkynylbenzaldehydes bearing various substitution patterns on the benzaldehyde and alkynyl units, the use of silver triflate (10 mol %) allowed a domino hydroarylation/cycloisomerization reaction process, leading to aryl-functionalized 1H-isochromene (>10 compounds, 80-98% yields). Notably, the reaction conditions were also compatible with benzaldehydes bearing an aliphatic-substituted alkynyl moiety with modest to good yields (34-88%, 10 compounds).

Bioinspired intramolecular diels-alder reaction: A rapid access to the highly-strained cyclopropane-fused polycyclic skeleton

A bioinsipred gold-catalyzed tandem Diels-Alder/Diels-Alder reaction of an enynal and a 1,3-diene, forming the highly-strained benzotricyclo[3.2.1.0 2,7]octane skeleton, was reported. In contrast, a Diels-Alder/Friedel-Crafts tandem reaction occurred instead when silver salts were used as the catalyst. Although both reactions experienced the similar Diels-Alder reaction of a pyrylium intermediate with a 1,3-diene, they have different reaction mechanisms. The former proceeded with a stepwise Diels-Alder reaction, while the latter one with a concerted one. Mother nature knows best! A gold-catalyzed reaction of enynals and 1,3-dienes, giving rapid access to the highly strained benzotricyclo[3.2.1.02,7]octane skeleton, is reported (see scheme; QMD=quinodimethane). Owing to the mild reaction conditions, excellent substrate scope, and high functional-group tolerance, this system holds potential for the construction of complex molecules with the tricyclo[3.2.1.02,7]octane skeleton. Copyright

Gold catalysis: β-ketonaphthalenes via molecular gymnastics of 1,6-diyne-4-en-3-ols

1,6-Diyne-4-en-3-ols with one terminal alkyne were applied as test substrates for a possible dual catalyzed cyclization. Instead of a dual catalysis cycle, naphthyl ketone derivatives were obtained as single products. The regioselectivity of the obtained products is unprecedented. Instead of the expected naphthyl ketones bearing the keto group in the α-position, the keto group is positioned in the ss-position of the naphthyl skeleton by a complex rearrangement of the starting materials. Copyright

Carbene transfer - A new pathway for propargylic esters in gold catalysis

Gold (homepage: http://www.hashmi.de) carbenes generated via 1,2-migration of a propargylic ester group can be transferred over a tethered alkyne. The use of aromatic backbones leads after a 1,7-carbene transfer to a benzyl-stabilized carbene as intermediate. A 1,2-shift of a methyl group delivers vinyl-substituted β-naphthol derivatives as the final products. Copyright

Grignard reagent/CuI/LiCl-mediated stereoselective cascade addition/cyclization of diynes: A novel pathway for the construction of 1-methyleneindene derivatives

Diynes containing a cyclopropane group smoothly undergo a novel intramolecular and stereoselective cascade addition/cyclization reaction to produce the corresponding 1-methyleneindene derivatives in moderate to good yields. This interesting transformation is mediated by Grignard reagent/CuI with LiCl as an additive under mild conditions. The obtained product can easily be further functionalized through cyclopropyl ring opening. A plausible reaction mechanism has also been presented on the basis of deuterium labeling and control experiments. Diyne cyclization: Diynes containing a cyclopropane group undergo a novel intramolecular and stereoselective cascade addition/cyclization reaction to produce the corresponding 1-methyleneindene derivatives (see scheme). The transformation proceeds under mild conditions and is promoted by a combination of Grignard reagent Copyright