Article
Chemistry, Multidisciplinary
Wen-Jun Yue, Ruben Martin
Summary: An alpha-difluoroalkylation reaction of benzyl amines with trifluoromethylarenes is described. The protocol offers simplicity, excellent chemoselectivity, and broad applicability, even with advanced synthetic intermediates, to access medicinally-relevant alpha-difluoroalkylated amines from easily accessible precursors.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Ling-Zhi Sun, Xuan Yang, Nan-Nan Li, Meng Li, Qin Ouyang, Jian-Bo Xie
Summary: A facile synthetic method for 4-aryl-4,5-dihydropyrrole-3-carboxylates has been developed using a rhodium-catalyzed ring expansion strategy. This method offers a novel mechanism and enables asymmetric catalytic synthesis with excellent diastereoselectivity, leading to the formation of substituted pyrrolidines.
Article
Chemistry, Organic
Jie Feng, Hui Liu, Yun Yao, Chong-Dao Lu
Summary: A series of alpha-mercapto-beta-amino acid derivatives were successfully synthesized through azaenolization of alpha-sulfanyl N-tert-butanesulfinylimidates and their nucleophilic addition to N-tosyl imines via a Mannich-type reaction. The resulting derivatives bearing a beta-sulfonylamino sulfide moiety participated in various inter- and intramolecular transformations.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Hu Tian, Hong-Ming Zhang, Liang Yin
Summary: In this article, a copper(I)-catalyzed asymmetric conjugate addition/protonation with selenols and alpha-substituted alpha,beta-unsaturated thioamides is described, which produces a series of chiral selenides with high to excellent enantioselectivity. The reaction shows a broad substrate scope for both selenols and alpha-substituted alpha,beta-unsaturated thioamides. The catalytic system is also successfully used for asymmetric selenation of beta-substituted alpha,beta-unsaturated thioamides. A [Cu-(R,R-P)-TANIAPHOS]-SePh species is identified by Se-77 NMR spectra, with a chemical shift at delta 462 ppm. Furthermore, a {[Cu-(R)-TOL-BINAP]-SePh}(2) species is characterized by X-ray analysis, confirming the formation of Cu-Se bond in the reaction. Finally, the straightforward transformations of the thioamide group to amine and thioester are demonstrated.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Daniel Rozsar, Alistair J. M. Farley, Iain McLauchlan, Benjamin D. A. Shennan, Ken Yamazaki, Darren J. Dixon
Summary: This article describes the enantioselective intermolecular conjugate addition of nitroalkanes to unactivated alpha,beta-unsaturated esters catalyzed by a bifunctional iminophosphorane (BIMP) superbase. It provides a straightforward approach to the synthesis of pharmaceutically relevant enantioenriched gamma-nitroesters with unprecedented selectivity. The methodology demonstrates broad substrate scope and has been successfully applied on a gram scale with reduced catalyst loading, allowing for catalyst recovery.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Yi-Wen Xie, Zhen-Ni Zhao, Zi-Wei Lin, Yu-Hao Wang, Ya-Qun Liu, Yi-Yong Huang
Summary: The Petasis reaction successfully synthesized alpha- and beta-butadienyl amines using (1S,2R)-1-amino-2-indanol as the substrate, demonstrating metal-free nature, broad substrate scope, complete regioselectivities, and high to excellent chirality induction. The favored nucleophilic addition across the Si-face of the imine intermediate was explained using DFT calculations of the six-membered chair-like transition state.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Kristina C. Probasco, Michael P. Jennings
Summary: The NXS-mediated halogenation reaction of (E)-alpha-trimethylsilyl-beta-alkyl(aryl)-alpha,beta-unsaturated esters in DMF resulted in the formation of (Z)-beta-substituted-alpha-halogenated-alpha,beta-unsaturated ester products with moderate to high yields. The reaction mechanism involves an initial halonium cation intermediate and regioselective ring opening with DMF, leading to the stereoselective formation of vinylic bromo- and chloroesters.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Changli He, Xiaoxue Tang, Xin He, Yuqiao Zhou, Xiaohua Liu, Xiaoming Feng
Summary: Reversal of regioselectivity in the catalytic asymmetric conjugate additions of 3-substituted oxindoles to beta-nitroenones or beta-nitroacrylates was achieved with chiral scandium catalysts. Functionalized 3,3-disubstituted oxindoles, including terminal and internal vinyl groups, were constructed in excellent yields and ee values.
CHINESE CHEMICAL LETTERS
(2023)
Article
Chemistry, Organic
Meng Li, Guang-Rui Peng, Xuan Yang, Zhen-Ning Ma, Jian-Bo Xie
Summary: We developed a copper-catalyzed enantio- and diastereoselective boron conjugate addition method for α-alkyl α,beta-unsaturated esters under base-free conditions. The approach exhibited excellent enantioselectivities and moderate to good conversions, although with moderate diastereoselectivities. The synthetic utility of this protocol was demonstrated.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Chang-Hong Liu, Jia-Ming Guo, Xin Li, Jian-Ting Sun, Bang-Guo Wei, Chang-Mei Si
Summary: An efficient method for accessing alpha-arylacetylene-substituted pyrrolidine and piperidine derivatives has been developed using a samarium diiodide-mediated addition-elimination process.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Kaizhi Li, Yixin Lu
Summary: Enantioselective gamma-addition of readily available alpha-substituted nitroacetates to allenoates has been achieved, providing a straightforward asymmetric synthesis of optically enriched alpha,alpha-disubstituted alpha-amino acid precursors. The reaction proceeds efficiently with high yields and good to excellent enantioselectivities in the presence of amino acid-derived phosphine catalysts, forming products containing a tetra-substituted stereogenic center.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Jiufeng Wu, Claire M. Young, Amy A. Watts, Alexandra M. Z. Slawin, Gregory R. Boyce, Michael Buhl, Andrew D. Smith
Summary: An enantioselective Michael addition of malonates to alpha,beta-unsaturated para-nitrophenyl esters was successfully achieved using the Lewis basic isothiourea HyperBTM as a catalyst.
Article
Chemistry, Organic
Yuya Nakagawa, Keigo Yamaguchi, Seijiro Hosokawa
Summary: The [3 + 2]-cycloaddition reaction between N-tosylaziridines and alpha,beta-unsaturated ketones was promoted with lithium iodide, providing high yields of the target products.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Jiahua Chen, Jun Wei Lim, Derek Yiren Ong, Shunsuke Chiba
Summary: The synthesis of alpha-tertiary amines was achieved by iteratively adding carbon nucleophiles to N,N-dialkyl carboxamides, forming anionic tetrahedral carbinolamine intermediates. These intermediates were then treated with bromotrimethylsilane followed by organomagnesium or organolithium reagents to produce alpha-tertiary amines. The use of (trimethylsilyl)methylmagnesium bromide as the second nucleophile allowed for aza-Peterson olefination, resulting in the formation of 1,1-diarylethylenes after acidic work-up.
Article
Chemistry, Organic
Yuan Zhou, Tong Xiong, Li-Yan Zhou, Hong-Yan Li, You-Cai Xiao, Fen-Er Chen
Summary: This paper reports the catalytic asymmetric synthesis of borylated 3-hydroxyoxindoles by addition of gem-diborylalkanes to isatins. Chiral 3-hydroxyoxindoles bearing two contiguous stereogenic centers were produced with high stereoselectivity and demonstrated synthetic utility through transformations of the boryl moiety.
Article
Chemistry, Organic
Eduardo Rodrigo, Ines Alonso, M. Belen Cid
Article
Chemistry, Multidisciplinary
Angel Manu Martinez, Ines Alonso, Nuria Rodriguez, Ramon Gomez Arrayas, Juan C. Carretero
CHEMISTRY-A EUROPEAN JOURNAL
(2019)
Article
Energy & Fuels
Y. Arroyo, M. A. Sanz-Tejedor, J. San Jose, L. A. Garcia-Escudero
Article
Energy & Fuels
Julio San Jose, Yolanda Arroyo, Maria Ascension Sanz-Tejedor
Article
Chemistry, Physical
Mario Martinez-Mingo, Andres Garcia-Viada, Ines Alonso, Nuria Rodriguez, Ramon Gomez Arrayas, Juan C. Carretero
Summary: The use of a removable N-(2-pyridyl)sulfonyl directing group provides a viable solution to overcome the limitation of blocking the more reactive gamma-position, allowing for the expansion of the scope of Pd-catalyzed delta-C-H arylation. This method is compatible with complex, multifunctional structures at either reaction partner. Experimental and density functional theory studies offer insights into the factors controlling site selectivity.
Article
Construction & Building Technology
J. F. San Jose Alonso, M. A. Sanz-Tejedor, Y. Arroyo, M. R. San Jose-Gallego
Summary: This study quantifies the air flow entering the operating room during the process of door opening and closing, and finds that sliding doors can reduce the entry of air from adjacent areas.
JOURNAL OF BUILDING ENGINEERING
(2022)
Article
Chemistry, Multidisciplinary
Mario Martinez-Mingo, Andres Garcia-Viada, Daniel Sowa Prendes, Ines Alonso, Nuria Rodriguez, Ramon Gomez Arrayas, Juan C. Carretero
Summary: The selective delta-C(sp(3))-H acetoxylation of N-(SO2Py)-protected amino acid derivatives has been achieved using palladium-catalysis and PhI(OAc)(2) as both oxidant and acetoxy source. The unique structural and electronic features of SO2Py are crucial in overriding the more favorable intramolecular C-H amination.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Energy & Fuels
A. Castellanos-Antolin, F. J. Rey-Martinez, L. J. San Jose-Gallego, Y. Arroyo-Gomez, J. M. Rey-Hernandez, J. F. San Jose-Alonso
Summary: This paper evaluates the energy savings achieved by introducing ventilation flow control and regulation systems in operating rooms of hospitals located in different climatic zones within Spain. Two control and regulation strategies of the air flow to be supplied and extracted in the operating rooms, during periods of inactivity, are studied. The results show significant energy savings.
Article
Chemistry, Organic
Emily L. Vargas, Mario Franco, Ines Alonso, Mariola Tortosa, M. Belen Cid
Summary: B(2)nep efficiently promotes N-O cleavage of nitrones to form imines in high yields via a simple, efficient, sustainable, functional group tolerant, and scalable protocol. The reaction occurs in the absence of additives through a concerted mechanism. We showed that DMPO and TEMPO, typically used as radical traps, are also deoxygenated by diboron reagents, revealing their limitations as mechanistic probes.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Marina Velado, Manuel Martinovic, Ines Alonso, Mariola Tortosa, Roberto Fernandez de la Pradilla, Alma Viso
Summary: The base-induced [2,3]-sigmatropic rearrangement of enantiopure 2-sulfinyl dienes has been optimized using NaH and iPrOH. The reaction proceeds through allylic deprotonation and sulfoxide-sulfenate rearrangement. The presence of a terminal allylic alcohol is crucial for achieving complete regioselectivity and high enantioselectivities.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Angel Manu Martinez, Alejandro Puet, Gema Dominguez, Ines Alonso, Rodrigo Castro-Biondo, Javier Perez-Castells
Summary: In this article, the use of cyclopropene as a dienophile for the intramolecular Diels-Alder vinylarene reaction (IMDAV) is described. The strain energy of cyclopropene is utilized to drive the reaction, resulting in good yields, excellent stereoselectivity, and broad functional tolerance. Theoretical calculations and NMR studies provide significant mechanistic insights.
Article
Multidisciplinary Sciences
Javier M. Rey-Hernandez, Yolanda Arroyo-Gomez, Julio F. San Jose-Alonso, Francisco J. Rey-Martinez
Summary: This study investigates the natural ventilation in a rural elementary school and its impact on thermal comfort and infection risk. The results show that the school has good natural ventilation, with temperature and humidity meeting regulatory requirements and low infection risk.
Article
Chemistry, Multidisciplinary
Christian Cristobal, Daniel Gavina, Ines Alonso, Maria Ribagorda, Juan C. Carretero, Carlos del Pozo, Javier Adrio
Summary: An enantioselective synthesis of polycyclic fluorinated pyrrolidines has been achieved by Cu-catalyzed intramolecular 1,3-dipolar cycloaddition. The method enables the formation of desired products with high yields and up to 99% enantiomeric excess, indicating the excellent activating role of fluoroalkyl substituents in this transformation.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Mario Martinez-Mingo, Ines Alonso, Nuria Rodriguez, Ramon Gomez Arrayas, Juan C. Carretero
Summary: Mechanistic insights into chemoselectivity control in Pd-catalyzed reactions have enabled the access to different heterocyclic frameworks from the same starting substrate by manipulating the reaction conditions.
CATALYSIS SCIENCE & TECHNOLOGY
(2021)