20565-86-0

Upstream product

• 64-17-5 ethanol 
• 591-50-4 iodobenzene 
• 14492-09-2 2-bromo-2-phenylacetaldehyde diethyl acetal 
• 64-67-5 diethyl sulfate 
• 122-78-1 phenylacetaldehyde 
• 536-74-3 phenylacetylene 
• 108-86-1 bromobenzene 
• 109-92-2 ethyl vinyl ether 
• 100-42-5 styrene 
• 83947-56-2 4,4,5,5-tetramethyl-2-((E)-styryl)-[1,3,2]dioxaborolane 

Downstream Products

• 369378-67-6 (S)-(2-ethoxy-2-methoxy-ethyl)-benzene 
• 85939-75-9 3,7-Diphenyl-8-methylpyrazolo<5,1-c><1,2,4>triazine 
• 130146-89-3 (2R^*,3R^*,4R^*)-2-ethoxy-4-(ethoxycarbonyl)-3-phenyl-1-(phenylsulfonyl)-1,2,3,4-tetrahydropyridine 
• 130146-89-3 (2R^*,3R^*,4S^*)-2-ethoxy-4-(ethoxycarbonyl)-3-phenyl-1-(phenylsulfonyl)-1,2,3,4-tetrahydropyridine 

Relevant academic research and scientific papers

H2-Acceptorless Dehydrogenative Boration and Transfer Boration of Alkenes Enabled by Zirconium Catalyst

The first example of an efficient and direct dehydrogenative boration of alkenes for vinyl boronate ester synthesis was achieved using a zirconium catalyst. Our methodology avoids using precious transition metals, additional hydrogen acceptors, high temperatures, and long reaction times, which were required to overcome the reducing ability of borane, to give alkyl boronate esters. Detailed mechanistic studies revealed a reversible reaction pathway and further suggested applying the zirconium complex as a “shuttle catalyst” for transfer boration, which thus sidesteps the use of relatively sensitive borane.

Synthesis of Piperidine Derivatives by Rhodium- Catalyzed Tandem Reaction of N-Sulfonyl-1,2,3-Triazole and Vinyl Ether

A chemoselective tandem reaction of 4-acyloxymethylene-1-sulfonyl-1,2,3-triazole and vinyl ether was reported, producing polysubstituted piperidine derivatives in up to 96% yield. The key intermediate N-sulfonyl 1-azadiene generated by migration of the OAc group to the α-imino rhodium carbene was isolated and a plausible mechanism was proposed. Several related ring systems were constructed from the highly functionalized products. (Figure presented.).

Interrogating Pd(II) Anion Metathesis Using a Bifunctional Chemical Probe: A Transmetalation Switch

Ligand metathesis of Pd(II) complexes is mechanistically essential for cross-coupling. We present a study of halide→OH anion metathesis of (Ar)PdII complexes using vinylBPin as a bifunctional chemical probe with Pd(II)-dependent cross-coupling pathways. We identify the variables that profoundly impact this event and allow control to be leveraged. This then allows control of cross-coupling pathways via promotion or inhibition of organoboron transmetalation, leading to either Suzuki-Miyaura or Mizoroki-Heck products. We show how this transmetalation switch can be used to synthetic gain in a cascade cross-coupling/Diels-Alder reaction, delivering borylated or non-borylated carbocycles, including steroid-like scaffolds.

Intermolecular Hydroalkoxylation of Terminal Alkynes Catalyzed by a Dipyrrinato Rhodium(I) Complex with Unusual Selectivity

An operationally simple and atom-economical method for the E-selective preparation of enol ethers is described. A novel dicarbonyl(5-phenyldipyrrinato)rhodium complex, 2, was prepared in four synthetic steps, characterized by X-ray crystallography and NMR

Rhodium-catalyzed anti-Markovnikov intermolecular hydroalkoxylation of terminal acetylenes

We report here the first transition-metal-catalyzed anti-Markovnikov intermolecular hydroalkoxylation of terminal acetylenes to give enol ethers in high yields without using bases. Arylacetylenes as well as alkenyl- and alkylacetylenes were coupled with aliphatic alcohols, and the products were obtained with high Z selectivity in most cases. Effective catalysts were 8-quinolinolato rhodium complexes, which are structurally simple but have been relatively unexplored as catalysts.

Synthesis of chiral acetals by asymmetric selenenylations

Asymmetric selenenylations of (E)-ethoxystyrene are described leading to chiral acetals. An efficient synthesis of such compounds including the determination of their absolute configuration is described.

Practical regioselective method for (E)-enol ehter

A new practical and highly regioselective synthetic method for (E)-enol ether is reported. (E)-enol ethers (E:Z = 93:7-99:1) were prepared from the corresponding enol acetates (E:Z?3:1) in two steps by bromination and anti- elimination of α-bromodialkylac

Solvolysis of styryliodonium salt: Products, rates, and mechanisms

The solvolysis of phenyl[(E)-styryl]iodonium tetrafluoroborate in various solvents was examined at 50-70°C by means of product and kinetic studies with the normal and labeled substrates. The reactions involved are α-elimination and substitutions with configurational retention and inversion. In methanol and ethanol, the main reaction is α-elimination, along with about 5% of substitution with the ratio of inversion/retention from 4/6 to 3/7. As the basicity of the solvent decreases, the reaction rate and the fraction of α-elimination decrease, and at the same time the ratio of inversion/retention of substitution also decreases. In 2,2,2- trifluoroethanol, only the substitution with retention was observed. Labeling experiments showed that complete isotope scrambling occurred between the olefinic hydrogens of the retained product while the deuterium remained at the original position of the inverted product. The substitution mechanism is concluded to involve parallel pathways: an S(N) 1-type with a vinylenebenzenium ion intermediate leading to retention and a vinylic S(N) 2- type with a direct attack by the nucleophilic solvent leading to inversion.

Palladium- or Nickel-Catalyzed Reactions of Alkenylmetals with Unsaturated Organic Halides as a Selective Route to Arylated Alkenes and Conjugated Dienes: Scope, Limitations, and Mechanism

Stereo- and regiodefined alkenylmetals containing Al, Zr, and Zn react with aryl and alkenyl iodides and bromides in the presence of catalytic amounts of Pd or Ni complexes containing phosphine ligands, such as PPh3, to give the corresponding cross-coupled products.Palladium catalysts permit nearly 100 percent stereospecificity in both alkenyl-aryl and alkenyl-alkenyl coupling reactions, whereas nickel catalysts lead to partial stereochemical scrambling in the alkenyl-alkenyl coupling.Although many other metals including Li, Mg, Cd, Hg, B, Si, Sn, Ti, and Ce were also used, the results were inferior to those obtained with Al, Zr, and Zn under the conditions used in the present study.The turnover numbers for the palladium-catalyzed reactions of PhI with (E)-1-octenylmetals containing Al, Zr, and Zn were 2,3, and > 2000 mmol of (E)-1-octenylbenzene (8) per mmol of Pd(PPh3)4 per hour at room temperature, respectively.The stoichiometric reaction of PhPd(PPh3)2I (6) with 1.2 equiv of (E)-1-octenylzinc chloride (7) in a 2:1 mixture of CD2Cl2 and THF was examined in detail.The reaction follows second-order konetics (k2 = 2.9 L/(mol.min) at 0 deg C) to give 8 without the buildup of any intermediate.The results are consistent with a slow formation of 9 via transmetalation followed by its rapid reductive elmination to give 8 and "Pd(PPhe3)2".Addition of PhI to the reaction mixture rapidly gives 6 in 98 percent yield, supporting the plausibility of the proposed oxidative addition step.These results are consistent with the proposed mechanism consisting of oxidative addition of Pd(0) complexes, rate-determining transmetalation involving Pd(II) complexes, and rapid decomposition of diorganopalladium(II) species to produce the coupling products in one or more subsequent steps.The rate-determining transmetalation step provides an explanation for the effect of metals in organometallic reagents used stoichiometrically.