210964-21-9

Upstream product

• 4525-50-2 nona-2,4-diyn-1-ol 
• 74-86-2 acetylene 
• 5159-41-1 2-iodobenzyl alcohol 
• 693-02-7 hex-1-yne 
• 106824-45-7 2-(hex-1-yn-1-yl)benzaldehyde 
• 6630-33-7 ortho-bromobenzaldehyde 
• 271769-81-4 (1,1-dimethylethyl)[(2-iodophenyl)methoxy]dimethylsilane 
• 88-67-5 2-Iodobenzoic acid 

Downstream Products

• 442904-00-9 o-n-hex-1-ynylbenzyl bromide 
• 106824-45-7 2-(hex-1-yn-1-yl)benzaldehyde 
• 947395-76-8 1-(1-azido-methyl)-2-hex-1-ynyl-benzene 
• 1449427-45-5 1-(hex-1-yn-1-yl)-2-({[(2E)-3-phenylprop-2-en-1-yl]oxy}methyl)benzene 
• 1449427-47-7 1-(hex-1-yn-1-yl)-2-[(prop-2-en-1-yloxy)methyl]benzene 
• 1449427-64-8 1-[(benzyloxy)methyl]-2-(hex-1-yn-1-yl)benzene 
• 568571-27-7 2-bromo-1-[2-(hex-1-ynyl)benzyl]-1H-indole-3-carboxaldehyde 

Relevant academic research and scientific papers

Regioselectivity Influences in Platinum-Catalyzed Intramolecular Alkyne O-H and N-H Additions

The steric and electronic drivers of regioselectivity in platinum-catalyzed intramolecular hydroalkoxylation are elucidated. A branch point is found that divides the process between 5-exo and 6-endo selective processes, and enol ethers can be accessed in good yields for both oxygen heterocycles. The main influence arises from an electronic effect, where the alkyne substituent induces a polarization of the alkyne that leads to preferential heteroatom attack at the more electron-deficient carbon. The electronic effects are studied in other contexts, including hydroacyloxylation and hydroamination, and similar trends in directionality are predominant although not uniformly observed.

An Oxyboration Route to a Single Regioisomer of Borylated Dihydrofurans and Isochromenes

An oxyboration reaction that employs B-O σ bonds as addition partners to C-C π bonds to form borylated dihydrofurans and isochromenes has been developed. By nature of the mechanism, the reaction produces exclusively one borylated regioisomer, in contrast to and/or complementary to alternative routes that produce these borylated heterocycles via C-H activation. Access to the borylative heterocyclization route is demonstrated from alcohols directly or from a hydroboration-oxyboration sequence starting from the corresponding ketone, forming the heterocyclic core and installing the boron in one synthetic step. Catechol boronates were directly used as coupling partners in the in situ Suzuki cross-coupling reactions without transesterification to pinacol boronates.

Synthesis of Functionalised 3-Isochromanones by Silylcarbocyclisation/Desilylation Reactions

A new protocol for the synthesis of 3-isochromanone derivatives based on rhodium-promoted silylcarbocyclisation reactions of ethynylbenzyl alcohol with different arylsilanes is described. The structure of the isochromanone depends upon the reaction condit

[3,3]-Sigmatropic rearrangement step in the gold-catalyzed cyclization of allyl-(ortho-alkinylphenyl)methyl ethers

The gold-catalyzed conversion of allyl-(ortho-alkynylphenyl)methyl ethers was investigated, and allylated isochromenes were obtained. An optimization of the catalysis conditions with respect to different phosphane and carbene ligands on gold, different counterions, and different solvents was conducted. Subsequently, the scope and limitations of this reaction were investigated with 21 substrates. The mechanistic studies show an allylic inversion, as supported by NMR data and an X-ray crystal structure analysis, as well as an intermolecular reaction, as determined by crossover experiments. There is no competition of protodeauration even in the presence of water. All these observations differ from other related conversions and clearly indicate product formation by a [3,3]sigmatropic rearrangement in the step forming the new C-C bond. The Golden Key: Allylic inversion and crossover experiments reveal a sigmatropic rearrangement as a key step in the gold-catalyzed intramolecular allyl transfer in ortho-alkinyl benzyl allyl ethers. Copyright

A simple and mild synthesis of 1H-isochromenes and (Z)-1-alkylidene-1,3- dihydroisobenzofurans by the iodocyclization of 2-(1-alkynyl)benzylic alcohols

(Chemical Equation Presented) A variety of iodo-substituted isochromenes, dihydroisobenzofurans, and pyranopyridines are readily prepared in good to excellent yields under mild conditions by the iodocyclization of readily available 2-(1-alkynyl)benzylic a

Iodine-mediated electrophilic cyclization of 2-alkynyl-1-methylene azide aromatics leading to highly substituted isoquinolines and its application to the synthesis of norchelerythrine

The reaction of 2-alkynyl-1-methylene azide aromatics 1 with iodine and/or other iodium donors, such as the Barluenga reagent (Py2IBF 4/HBF4) and NIS, gave highly substituted cyclization products, namely, the 1,3-disubstituted 4-iodoisoquinolines 2, in good to high yields. Not only simple 2-alkynyl benzyl azides 1a-j and their substituted analogues 1k-u and 6 but also heteroaromatic analogues, including pyridine 8, pyrroles 10a-c, furane 10d, and thiophenes 10e-g, gave the corresponding isoquinoline derivatives in excellent to allowable yields. Electron-donating and electron-accepting substituents on the aromatic ring were equally tolerated, and either acidic or basic (or even neutral) reaction conditions, depending on the reactivity of the substrate, could be applied to smoothly convert the azide starting materials into the desired isoquinoline products in moderate to good yields. Limits were found only in connection with the substituent at the alkyne terminus, where electron-neutral or electron-donating substituents are clearly favored. The iodine-mediated electrophilic cyclization of 1 most probably proceeds through the iodonium ion intermediate 4 followed by nucleophilic cyclization of the azide and subsequent elimination of N2. This new methodology was successfully applied to the short synthesis of norchelerythrine.

Synthesis of 1,3,4-trisubstituted isoquinolines by iodine-mediated electrophilic cyclization of 2-alkynyl benzyl azides

(Chemical Equation Presented) The I's have it: A series of 2-alkynyl benzyl azides have been smoothly converted into 1,3,4-trisubstituted isoquinolines in moderate to excellent yields by an iodonium-mediated synthesis (see scheme). Depending on the struct

Palladium-catalyzed esterification-hydroarylation reactions of 2-alkynyl-benzaldehydes with aryl iodides in methanol

The reaction of 2-alkynylbenzaldehydes with aryl iodides in the presence of Pd(PPh3)4 and K2CO3 in refluxing methanol for 24 hours gave the dehydrogenation-addition products, methyl 2-(2,2-disubstituted-vinyl)benzoates in modest yields; together with the cyclization products, 3-methoxy-1-monosubstituted-methylene-3- hydroisobenzofurans in 3-18% yields.

Versatile synthesis of (Z)-1-alkylidene-1,3-dihydroisobenzofurans and 1H-isochromenes by palladium-catalyzed cycloisomerization of 2-alkynylbenzyl alcohols

An easy synthesis of (Z)-1-alkylidene-1,3-dihydroisobenzofurans and 1H-isochromenes by palladium-catalyzed cycloisomerization of readily available 2-alkynylbenzyl alcohols under neutral conditions is reported. Reactions were carried out at 70-100°C in the

Synthesis of annulated γ-carbolines and heteropolycycles by the palladium-catalyzed intramolecular annulation of alkynes

A variety of N-substituted 2-bromo-1H-indole-3-carboxaldehydes incorporating an alkyne-containing tether on the indole nitrogen have been converted to the corresponding tert-butylimines, which have been subjected to palladium-catalyzed intramolecular imin