13724-78-2Relevant academic research and scientific papers
Electrochemical Fluorination of Vinyl Boronates through Donor-Stabilized Vinyl Carbocation Intermediates**
Wigman, Benjamin,Lee, Woojin,Wei, Wenjing,Houk, Kendall N.,Nelson, Hosea M.
, (2022/02/10)
The electrochemical generation of vinyl carbocations from alkenyl boronic esters and boronates is reported. Using easy-to-handle nucleophilic fluoride reagents, these intermediates are trapped to form fully substituted vinyl fluorides. Mechanistic studies support the formation of dicoordinated carbocations through sequential single-electron oxidation events. Notably, this electrochemical fluorination features fast reaction times and Lewis acid-free conditions. This transformation provides a complementary method to access vinyl fluorides with simple fluoride salts such as TBAF.
Palladium catalyzed carbonylative generation of potent, pyridine-based acylating electrophiles for the functionalization of arenes to ketones
Arndtsen, Bruce A.,Kaiser, Angela M.,Liu, Yi
, p. 8610 - 8616 (2020/09/07)
We describe here the design of a palladium catalyzed route to generate aryl ketones via the carbonylative coupling of (hetero)arenes and aryl- or vinyl-triflates. In this, the use of the large bite angle Xantphos ligand on palladium provides a unique avenue to balance the activation of the relatively strong C(sp2)-OTf bond with the ultimate elimination of a new class of potent Friedel-Crafts acylating agent: N-acyl pyridinium salts. The latter can be exploited to modulate reactivity and selectivity in carbonylative arene functionalization chemistry, and allow the efficient synthesis of ketones with a diverse array of (hetero)arenes. This journal is
Enones from Acid Fluorides and Vinyl Triflates by Reductive Nickel Catalysis
Pan, Feng-Feng,Guo, Peng,Li, Chun-Ling,Su, Peifeng,Shu, Xing-Zhong
supporting information, p. 3701 - 3705 (2019/05/24)
A nickel-catalyzed reductive coupling between acid fluorides and vinyl triflates has been described. This method provides an efficient access to various enones and avoids the requirement for acyl or vinyl metallic reagents in the conventional approaches.
The photo-nazarov reaction: Scope and application
Cai, Shujun,Xiao, Zheming,Shi, Yingbo,Gao, Shuanhu
supporting information, p. 8677 - 8681 (2014/07/21)
The reaction conditions and scope of the photo-Nazarov reaction of aryl vinyl ketones were investigated. In contrast to the conventional acid-catalyzed methods, this photolytic electrocyclization proceeds in the neutral or basic conditions. Irradiating substrates bearing various aromatic rings, acid-sensitive groups, cyclohexenyl, cycloheptenyl, and unsaturated pyran with UV-light (254 nm) smoothly yielded hexahydrofluorenones and related structures. This photo-Nazarov reaction could also be applicable to the substrates carrying β-alkyl groups on the enone, which gave corresponding polycyclic rings containing quaternary centers. These photo-electrocyclized products may prove useful for synthesizing a variety of natural products and their derivatives. Further application of this mild photo-Nazarov reaction in the synthesis of taiwaniaquinol B was achieved.
Indium(III)-catalyzed coupling between alkynes and aldehydes to α,β-unsaturated ketones
Miura, Katsukiyo,Yamamoto, Kiyomi,Yamanobe, Aya,Ito, Keisuke,Kinoshita, Hidenori,Ichikawa, Junji,Hosomi, Akira
, p. 766 - 767 (2011/01/09)
The combined use of a catalytic amount of InX3 (X = OTf and NTf2) and 1-butanol was found to be effective in formal alkynealdehyde metathesis. With this catalytic system, aromatic alkynes reacted with aromatic aldehydes to give chalcones in moderate to good yields. Alkynals were efficiently converted into 5- to 7-membered cyclic compounds by intramolecular alkyne-aldehyde coupling.
Nickel-catalyzed carbonylative Negishi cross-coupling reactions
Wang, Qiaoling,Chen, Chuo
, p. 2916 - 2921 (2008/09/21)
Catalytic carbonylative Negishi cross-coupling reactions are described. This method readily provides various enones from enol triflates and diorganozinc reagents with catalytic amounts of nickel(II) chloride-4,4′-dimethoxyl-2,2′-bipyridyl under carbon mon
Diaryl-dialkyl-substituted pyrazoles: Regioselective synthesis and binding affinity for the estrogen receptor
Nishiguchi, Gisele A.,Rodriguez, Alice L.,Katzenellenbogen, John A.
, p. 947 - 950 (2007/10/03)
We have developed two novel series of tetrasubstituted pyrazoles, embodying 1,3-diaryl-4,5-dialkyl or 3,5-diaryl-1,4-dialkyl substitution patterns. The scope of a regioselective method, developed by us earlier, was expanded to allow the synthesis of the first series of these tetrasubstituted pyrazoles directly from α,β-unsaturated ketones. The binding affinity of some of these pyrazoles for the estrogen receptor (ER) subtypes ERα and ERβ is very high, and the overall affinity pattern suggests the importance of three phenol substituents for high affinity, ERα-selective binding.
