15619-32-6Relevant academic research and scientific papers
Three-Component Difunctionalization of Cyclohexenyl Triflates: Direct Access to Versatile Cyclohexenes via Cyclohexynes
Cho, Seoyoung,McLaren, E. J.,Wang, Qiu
, p. 26332 - 26336 (2021/11/10)
Difunctionalization of strained cyclic alkynes presents a powerful strategy to build richly functionalized cyclic alkenes in an expedient fashion. Herein we disclose an efficient and flexible approach to achieve carbohalogenation, dicarbofunctionalization, aminohalogenation and aminocarbonation of readily available cyclohexenyl triflates. We have demonstrated the novel use of zincate base/nucleophile system for effective formation of key cyclohexyne intermediates and selective addition of various carbon and nitrogen nucleophiles. Importantly, leveraging the resulting organozincates enables the incorporation of a broad range of electrophilic partners to deliver structurally diverse cyclohexene motifs. The importance and utility of this method is also exemplified by the modularity of this approach and the ease in which even highly complex polycyclic scaffolds can be accessed in one step.
Palladium-Catalyzed Asymmetric Tandem Denitrogenative Heck/Tsuji-Trost of Benzotriazoles with 1,3-Dienes
Li, Yin-Lin,Wu, Hai-Hong,Zhang, Junliang,Zhang, Pei-Chao
, p. 13010 - 13015 (2021/09/07)
The asymmetric denitrogenative cycloaddition has emerged as a powerful tool to build chiral aza-heterocyles. However, only one example of asymmetric denitrogenative cycloaddition of benzotriazole with unsaturated hydrocarbons has been explored so far, bec
Catalytic (3+2) Palladium-Aminoallyl Cycloaddition with Conjugated Dienes
Trost, Barry M.,Huang, Zhongxing
supporting information, p. 6396 - 6399 (2019/04/13)
We describe the design and application of tailored aminoallyl precursors for catalytic (3+2) cycloaddition with conjugated dienes via a Pd-aminoallyl intermediate. The new cycloaddition reactions override the conventional (4+3) selectivity of aminoallyl cation cycloaddition through a sequence of Pd-allyl transfer and ring closure. A variety of highly substituted or fused pyrrolidine rings were synthesized using the cycloaddition, and can further undergo [1,3] N-to-C rearrangement to five-membered carbocycles with a different palladium catalyst. The utility of the (3+2) cycloaddition is also demonstrated by the preparation of various derivatives from the bicyclic pyrrolidine products.
IBS-catalyzed oxidative rearrangement of tertiary allylic alcohols to enones with oxone
Uyanik, Muhammet,Fukatsu, Ryota,Ishihara, Kazuaki
supporting information; experimental part, p. 3470 - 3473 (2009/12/05)
A 2-iodoxybenzenesulfonic acid (IBS)-catalyzed oxidative rearrangement of tertiary allylic alcohols to enones with powdered Oxone in the presence of potassium carbonate and tetrabutylammonium hydrogen sulfate has been developed.
Oxidative rearrangement of tertiary allylic alcohols employing oxoammonium salts
Shibuya, Masatoshi,Tomizawa, Masaki,Iwabuchi, Yoshiharu
, p. 4750 - 4752 (2008/09/20)
(Chemical Equation Presented) Practical and highly efficient methods for oxidative rearrangement of tertiary allylic alcohols to β-substituted α,β-unsaturated carbonyl compounds employing oxoammonium salts are described. The methods developed are applicable to acyclic substrates as well as medium membered ring substrates and macrocyclic substrates. The counteranion of the oxoammonium salt plays crucial roles on this oxidative rearrangement.
Oxidative rearrangement of cyclic tertiary allylic alcohols with IBX in DMSO
Shibuya, Masatoshi,Ito, Shinichiro,Takahashi, Michiyasu,Iwabuchi, Yoshiharu
, p. 4303 - 4306 (2007/10/03)
(Chemical Equation Presented) A practical and environmentally friendly method for oxidative rearrangement of five- and six-membered cyclic tertiary allylic alcohols to β-disubstituted α,β-unsaturated ketones by the IBX/DMSO reagent system is described. Several conventional protecting groups (e.g., Ac, MOM, and TBDPS) are compatible under the reaction conditions prescribed.
Competitive Reactions of Diene Cation Radicals Formed on Irradiated Metal Oxide Surfaces
Fox, Marye Anne,Sackett, Debra D.,Younathan, Janet N.
, p. 1643 - 1660 (2007/10/02)
The heterogeneous photochemical oxygenation of conjugated dienes induced by long wavelength UV irradiation of TiO2 powders suspended in oxygenated CH3CN was studied.In nearly all cases, products resulting from the oxidative cleavage of the double bonds were observed, in parallel to that previously reported for monoolefins.A mechanism is proposed which involves the intermediacy of a diene cation radical generated by transfer of an electron from the adsorbed diene to a photogenerated hole localized at the surface of the excited TiO2 particle.Non-oxidative cleavage products are also observed, and the effect of the semiconductor surface in controlling reactivity of the photogenerated cation radical is discussed.The first examples of aromatization and Diels-Alder dimerization mediated by irradiated semiconductor suspensions are presented.
CYCLO-CODIMERIZATION OF 1,3-BUTADIENE DERIVATIVES WITH NON-ACTIVATED TERMINAL ACETYLENES CATALYZED BY CATIONIC RHODIUM(I) COMPLEX
Matsuda, Isamu,Shibata, Masahiro,Sato, Susumu,Izumi, Yusuke
, p. 3361 - 3362 (2007/10/02)
An efficient cyclo-codimerization between 1,3-diene and non-activated terminal acetylene has been attained by the catalysis of PF6 to give 1,4-disubstituted cyclohexa-1,3-dienes under mild conditions.
Reductive displacement of allylic acetates by hydride transfer via catalytic activation by palladium(0) complexes
Hutchins, Robert O.,Learn, Keith,Fulton, Robert P.
, p. 27 - 30 (2007/10/02)
Allylic acetates are reduced to alkenes by reductive displacement by hydride reagents via catalytic activation with Pd(0) complexes. In the absence of hydrides, allylic acetates afford conjugated dienes in DMSO solvent.
