78388-19-9Relevant academic research and scientific papers
Twofold Radical-Based Synthesis of N, C-Difunctionalized Bicyclo[1.1.1]pentanes
Anderson, Edward A.,Mousseau, James. J.,Nugent, Jeremy,Owen, Benjamin,Pickford, Helena D.,Smith, Russell C.
supporting information, p. 9729 - 9736 (2021/07/19)
Bicyclo[1.1.1]pentylamines (BCPAs) are of growing importance to the pharmaceutical industry as sp3-rich bioisosteres of anilines and N-tert-butyl groups. Here we report a facile synthesis of 1,3-disubstituted BCPAs using a twofold radical functionalization strategy. Sulfonamidyl radicals, generated through fragmentation of α-iodoaziridines, undergo initial addition to [1.1.1]propellane to afford iodo-BCPAs; the newly formed C-I bond in these products is then functionalized via a silyl-mediated Giese reaction. This chemistry also translates smoothly to 1,3-disubstituted iodo-BCPs. A wide variety of radical acceptors and iodo-BCPAs are accommodated, providing straightforward access to an array of valuable aniline-like isosteres.
Copper-Catalyzed Azide–Ynamide Cyclization to Generate α-Imino Copper Carbenes: Divergent and Enantioselective Access to Polycyclic N-Heterocycles
Chen, Yang-Bo,Deng, Chao,Liu, Rai-Shung,Liu, Xin,Luo, Chen,Wang, Ze-Shu,Ye, Long-Wu,Zhai, Tong-Yi,Zhang, Yi-Ping
, p. 17984 - 17990 (2020/08/21)
Here an efficient copper-catalyzed cascade cyclization of azide-ynamides via α-imino copper carbene intermediates is reported, representing the first generation of α-imino copper carbenes from alkynes. This protocol enables the practical and divergent synthesis of an array of polycyclic N-heterocycles in generally good to excellent yields with broad substrate scope and excellent diastereoselectivities. Moreover, an asymmetric azide–ynamide cyclization has been achieved with high enantioselectivities (up to 98:2 e.r.) by employing BOX-Cu complexes as chiral catalysts. Thus, this protocol constitutes the first example of an asymmetric azide–alkyne cyclization. The proposed mechanistic rationale for this cascade cyclization is further supported by theoretical calculations.
Synthesis of 1,2-Dihydroquinolines via Hydrazine-Catalyzed Ring-Closing Carbonyl-Olefin Metathesis
Zhang, Yunfei,Sim, Jae Hun,Macmillan, Samantha N.,Lambert, Tristan H.
supporting information, p. 6026 - 6030 (2020/08/05)
The synthesis of 1,2-dihydroquinolines by the hydrazine-catalyzed ring-closing carbonyl-olefin metathesis (RCCOM) of N-prenylated 2-aminobenzaldehydes is reported. Substrates with a variety of substitution patterns are shown. With an acid-labile protecting group on the nitrogen atom, in situ deprotection and autoxidation furnish quinoline. In comparison with related oxygen-containing substrates, the cycloaddition step of the catalytic cycle is shown to be slower, but the cycloreversion is found to be more facile.
AuCl3-Catalyzed Ring-Closing Carbonyl–Olefin Metathesis
Wang, Rui,Chen, Yi,Shu, Mao,Zhao, Wenwen,Tao, Maoling,Du, Chao,Fu, Xiaoya,Li, Ao,Lin, Zhihua
supporting information, p. 1941 - 1946 (2020/02/11)
Compared with the ripeness of olefin metathesis, exploration of the construction of carbon–carbon double bonds through the catalytic carbonyl–olefin metathesis reaction remains stagnant and has received scant attention. Herein, a highly efficient AuCl3-catalyzed intramolecular ring-closing carbonyl–olefin metathesis reaction is described. This method features easily accessible starting materials, simple operation, good functional-group tolerance and short reaction times, and provides the target cyclopentenes, polycycles, benzocarbocycles, and N-heterocycle derivatives in good to excellent yields.
Visible-Light Mediated Hydrosilylative and Hydrophosphorylative Cyclizations of Enynes and Dienes
Chen, Xiaoyun,Hou, Hong,Shi, Yaocheng,Xu, Yue,Yan, Chaoguo,Yang, Haibo,Zhu, Shaoqun
supporting information, (2020/03/04)
Described herein is a visible-light mediated intermolecular radical cyclization approach to access heterocycles. Heteroatom radicals, such as silicon and phosphorus atom radicals, were generated via direct hydrogen atom abstraction by the photoexcited catalyst species with hydro-silanes and phosphine oxides. The radical addition/cyclization/HAT (hydrogen atom transfer) reaction sequences of 1,6-enynes and 1,6-dienes were highly efficient delivering the desired heterocycles in good yields.
Unprecedented nucleophile-promoted 1,7-S or Se shift reactions under Pummerer reaction conditions of 4-alkenyl-3-sulfinylmethylpyrroles
Go, Takashi,Morimatsu, Akane,Wasada, Hiroaki,Tanabe, Genzoh,Muraoka, Osamu,Sawada, Yoshiharu,Yoshimatsu, Mitsuhiro
, p. 2722 - 2729 (2018/11/21)
A unique 1,7-S- and Se-shift reaction under Pummerer reaction conditions of 4-alkenyl-3-sulfinyl- and seleninylpyrroles was described. The usual Pummerer reaction of 4-(alkenylaminomethyl)-3-phenylsulfinylpyrroles and a successive reaction with tetrabutyl
Domino Aryne Annulation via a Nucleophilic-Ene Process
Xu, Hai,He, Jia,Shi, Jiarong,Tan, Liang,Qiu, Dachuan,Luo, Xiaohua,Li, Yang
supporting information, p. 3555 - 3559 (2018/03/21)
1,2-Benzdiyne equivalents possess the unique property that they can react with two arynophiles through iteratively generated 1,2- and 2,3-aryne intermediates. Upon rational modification on the second leaving group of these aryne precursors, a domino aryne annulation approach was developed through a nucleophilic-ene reaction sequence. Various benzo-fused N-heterocyclic frameworks were achievable under transition metal-free conditions with a broad substrate scope.
Palladium-Catalyzed Intermolecular Oxidative Cyclization of Allyltosylamides with AcOH: Assembly of 3-Pyrrolin-2-ones
Huang, Jiuzhong,Zheng, Jia,Wu, Wanqing,Li, Jianxiao,Ma, Zhiqiang,Ren, Yanwei,Jiang, Huanfeng
, p. 8191 - 8198 (2017/08/14)
The first example of Pd-catalyzed oxidative cyclization of allyltosylamides with acetic acid is reported. This transformation involved C-N/C-C bond formation and provided 3-pyrrolin-2-ones in a one-pot manner with easy-operation, excellent atom economy and good yields. Mechanistic studies indicate that the reaction proceeds through intermolecular aminopalladation, migratory insertion, reinsertion and β-hydride elimination processes.
Silver(I)-Catalyzed Deprenylation of Allylsulfonamide Derivatives
Inagaki, Fuyuhiko,Hira, Shisen,Mukai, Chisato
supporting information, p. 2143 - 2146 (2017/09/26)
The silver(I)-catalyzed deprenylation of sulfonamide bearing prenyl functional groups on the nitrogen atom has been developed. In this reaction, the prenyl moiety was selectively eliminated without allyl or benzyl cleavage on the nitrogen atom. In addition, geranyl was also applicable for this elimination reaction. Furthermore, sulfonamide possessing two prenyl groups underwent a double deprenylation to form the corresponding deprenylated sulfonamide. Thus, a novel reactivity between the silver cation and double bond was observed.
A New Approach to Non-Coordinating Anions: Lewis Acid Enhancement of Porphyrin Metal Centers in a Zwitterionic Metal-Organic Framework
Johnson, Jacob A.,Petersen, Brenna M.,Kormos, Attila,Echeverría, Elena,Chen, Yu-Sheng,Zhang, Jian
supporting information, p. 10293 - 10298 (2016/09/03)
We describe a new strategy to generate non-coordinating anions using zwitterionic metal-organic frameworks (MOFs). By assembly of anionic inorganic secondary building blocks (SBUs) ([In(CO2)4]-) with cationic metalloporphyrin-based organic linkers, we prepared zwitterionic MOFs in which the complete internal charge separation effectively prevents the potential binding of the counteranion to the cationic metal center. We demonstrate the enhanced Lewis acidity of MnIII- and FeIII-porphyrins in the zwitterionic MOFs in three representative electrocyclization reactions: [2 + 1] cycloisomerization of enynes, [3 + 2] cycloaddition of aziridines and alkenes, and [4 + 2] hetero-Diels-Alder cycloaddition of aldehydes with dienes. This work paves a new way to design functional MOFs for tunable chemical catalysis.
