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1.
Reversible Dimerization of Phosphine‐Stabilized Silylenes by Silylene Insertion into SiII–H and SiII–Cl σ‐Bonds at Room Temperature
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Dr. Ricardo Rodriguez Dr. Yohan Contie Dr. Yanli Mao Dr. Nathalie Saffon‐Merceron Dr. Antoine Baceiredo Prof. Vicenç Branchadell Dr. Tsuyoshi Kato 《Angewandte Chemie (International ed. in English)》2015,54(50):15276-15279
Contrary to the classical silylene dimerization leading to a disilene structure, phosphine stabilized hydro‐ and chloro‐silylenes ( 2 a , b ) undergo an unique dimerization via silylene insertion into Si? X σ‐bonds (X=H, Cl), which is reversible at room temperature. DFT calculations indicate that the insertion reaction proceeds in one step in a concerted manner. 相似文献
2.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(45):14460-14464
Highly enantioselective cycloisomerization of N ‐methylanilines, bearing o ‐alkenyl groups, into indolines is established. An iridium catalyst bearing a bidentate chiral diphosphine effectively promotes the intramolecular addition of the C(sp3)−H bond across a carbon–carbon double bond in a highly enantioselective fashion. The reaction gives indolines bearing a quaternary stereogenic carbon center at the 3‐position. The reaction mechanism involves rate‐determining oxidative addition of the N ‐methyl C−H bond, followed by intramolecular carboiridation and subsequent reductive elimination. 相似文献
3.
A DFT Study on the Conversion of Aryl Iodides to Alkyl Iodides: Reductive Elimination of R−I from Alkylpalladium Iodide Complexes with Accessible β‐Hydrogens
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Wei Hao Junnian Wei Yue Chi Prof. Dr. Patrick J. Walsh Prof. Dr. Zhenfeng Xi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(10):3422-3429
DFT calculations have been performed on the palladium‐catalyzed carboiodination reaction. The reaction involves oxidative addition, alkyne insertion, C?N bond cleavage, and reductive elimination. For the alkylpalladium iodide intermediate, LiOtBu stabilizes the intermediate in non‐polar solvents, thus promoting reductive elimination and preventing β‐hydride elimination. The C?N bond cleavage process was explored and the computations show that PPh3 is not bound to the Pd center during this step. Experimentally, it was demonstrated that LiOtBu is not necessary for the oxidative addition, alkyne insertion, or C?N bond cleavage steps, lending support to the conclusions from the DFT calculations. The turnover‐limiting steps were found to be C?N bond cleavage and reductive elimination, whereas oxidative addition, alkyne insertion, and formation of the indole ring provide the driving force for the reaction. 相似文献
4.
Hong Yi Wenbin Mao Martin Oestreich 《Angewandte Chemie (International ed. in English)》2019,58(11):3575-3578
An enantioselective C(sp3)?C(sp3) cross‐coupling of racemic α‐silylated alkyl iodides and alkylzinc reagents is reported. The reaction is catalyzed by NiCl2/(S,S)‐Bn‐Pybox and yields α‐chiral silanes with high enantiocontrol. The catalyst system does not promote the cross‐coupling of the corresponding carbon analogue, corroborating the stabilizing effect of the silyl group on the alkyl radical intermediate (α‐silicon effect). Both coupling partners can be, but do not need to be, functionalized, and hence, even α‐chiral silanes with no functional group in direct proximity of the asymmetrically substituted carbon atom become accessible. This distinguishes the new method from established approaches for the synthesis of α‐chiral silanes. 相似文献
5.
Ming Gong Prof. Dr. Jing‐Mei Huang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(40):14293-14296
A mild method for the direct C?H/N?H coupling between γ‐lactams and anilines through electrochemical oxidation has been developed. The protocol proceeded smoothly without metal catalysts at room temperature to afford γ‐substituted γ‐lactams in good yields. It has been revealed that the quasi‐divided cell which provided high current density on the anode was crucial for this reaction. 相似文献
6.
Yu‐Li Sun Xing‐Ben Wang Feng‐Na Sun Qian‐Qian Chen Jian Cao Zheng Xu Li‐Wen Xu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(20):6819-6823
A palladium‐catalyzed enantioselective intramolecular σ‐bond cross‐exchange between C?I and C?C bonds is realized, providing chiral indanones bearing an alkyl iodide group and an all‐carbon quaternary stereocenter. Pd/TADDOL‐derived phosphoramidite is found to be an efficient catalytic system for both C?C bond cleavage and alkyl iodide reductive elimination. In addition to aryl iodides, aryl bromides can also be used for this transformation in the presence of KI. Density‐functional theory (DFT) calculation studies support the ring‐opening of cyclobutanones occuring through an oxidative addition/reductive elimination process involving PdIV species. 相似文献
7.
Sterically Congested 2,6‐Disubstituted Anilines from Direct C−N Bond Formation at an Iodine(III) Center
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Nicola Lucchetti Dr. Michelangelo Scalone Dr. Serena Fantasia Prof. Dr. Kilian Muñiz 《Angewandte Chemie (International ed. in English)》2016,55(42):13335-13339
2,6‐Disubstituted anilines are readily prepared from the direct reaction between amides and diaryliodonium salts. As demonstrated for 24 different examples, the reaction is of unusually broad scope with respect to the sterically congested arene and the nitrogen source, occurs without the requirement for any additional promoter, and proceeds through a direct reductive elimination at the iodine(III) center. The efficiency of the coupling procedure is further demonstrated within the short synthesis of a chemerin binding inhibitor. 相似文献
8.
Jelte S. Steen Gerald Knizia Johannes E. M. N. Klein 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(37):13267-13273
Reductive elimination is an elementary organometallic reaction step involving a formal oxidation state change of ?2 at a transition‐metal center. For a series of formal high‐valent NiIV complexes, aryl–CF3 bond‐forming reductive elimination was reported to occur readily (Bour et al. J. Am. Chem. Soc. 2015 , 137, 8034–8037). We report a computational analysis of this reaction and find that, unexpectedly, the formal NiIV centers are better described as approaching a +II oxidation state, originating from highly covalent metal–ligand bonds, a phenomenon attributable to σ‐noninnocence. A direct consequence is that the elimination of aryl–CF3 products occurs in an essentially redox‐neutral fashion, as opposed to a reductive elimination. This is supported by an electron flow analysis which shows that an anionic CF3 group is transferred to an electrophilic aryl group. The uncovered role of σ‐noninnocence in metal–ligand bonding, and of an essentially redox‐neutral elimination as an elementary organometallic reaction step, may constitute concepts of broad relevance to organometallic chemistry. 相似文献
9.
A Free‐Radical‐Promoted Stereospecific Decarboxylative Silylation of α,β‐Unsaturated Acids with Silanes
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Lizhi Zhang Zhaojia Hang Prof. Dr. Zhong‐Quan Liu 《Angewandte Chemie (International ed. in English)》2016,55(1):236-239
A stereospecific decarboxylative silylation of acrylic and propiolic acids with silanes was developed. This reaction represents the first example of decarboxylative C? Si bond formation and provides an efficient and convenient approach to various synthetically useful alkenyl and alkynyl organosilicon compounds through the reaction of α,β‐unsaturated acids with silanes. Spin‐trapping and EPR experiments support a radical addition/elimination process. 相似文献
10.
Nadine E. Poitiers Dr. Volker Huch Dr. Michael Zimmer Prof. Dr. David Scheschkewitz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(70):16599-16602
Reactions of silylenes with heavier chalcogens (E) typically result in Si=E double bonds or their π-addition products. In contrast, the oxidation of a silylene-functionalized unsaturated silicon cluster (siliconoid) with Group 16 elements selectively yields cluster expanded siliconoids Si7E (E=S, Se, Te) fully preserving the unsaturated nature of the cluster scaffold as evident from the NMR signatures of the products. Mechanistic considerations by DFT calculations suggest the intermediacy of a Si6 siliconoid with exohedral Si=E functionality. The reaction thus may serve as model system for the oxidation of surface-bonded silylenes at Si(100) by chalcogens and their diffusion into the silicon bulk. 相似文献
11.
This report presents the first example of nickel‐catalyzed mild decarboxylative cross‐coupling reaction for the regioselective formation of C–Si bond. An easily accessible and significantly stable Ni (dmg)2 owes the role of key promoter. This reaction is highly functional group tolerant and offers α,β‐unsaturated silanes in synthetically useful yields. The reaction gives access to the successful utilization of otherwise difficult trialkyl silanes as coupling partners and operates at a moderate temperature, which is beneficial to deal with highly volatile silanes. 相似文献
12.
Hydroarylation of bicyclic alkenes has been developed using a low‐valent ReI‐catalyzed, directing group‐assisted C?H bond activation strategy. The addition of sodium acetate significantly improves the reaction efficiency; moreover, bicyclic alkenes such as 7‐oxa and aza benzonorbornadienes worked efficiently under this reaction condition. Preliminary mechanistic studies suggest that, after the alkene insertion, the rhenacycle preferentially undergoes protonolysis rather than reductive elimination. 相似文献
13.
Divergent Total Syntheses of Enmein‐Type Natural Products: (−)‐Enmein, (−)‐Isodocarpin,and (−)‐Sculponin R
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Saiyong Pan Sicong Chen Guangbin Dong 《Angewandte Chemie (International ed. in English)》2018,57(21):6333-6336
Divergent total syntheses of the enmein‐type natural products (?)‐enmein, (?)‐isodocarpin, and (?)‐sculponin R have been achieved in a concise fashion. Key features of the strategy include 1) an efficient early‐stage cage formation to control succeeding diastereoselectivity, 2) a one‐pot acylation/akylation/lactonization to construct the C‐ring and C8 quarternary center, 3) a reductive alkenylation approach to construct the enmain D/E rings and 4) a flexible route to allow divergent syntheses of three natural products. 相似文献
14.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2018,130(21):6441-6444
Divergent total syntheses of the enmein‐type natural products (−)‐enmein, (−)‐isodocarpin, and (−)‐sculponin R have been achieved in a concise fashion. Key features of the strategy include 1) an efficient early‐stage cage formation to control succeeding diastereoselectivity, 2) a one‐pot acylation/akylation/lactonization to construct the C‐ring and C8 quarternary center, 3) a reductive alkenylation approach to construct the enmain D/E rings and 4) a flexible route to allow divergent syntheses of three natural products. 相似文献
15.
Cong Tian Leonardo Massignan Tjark H. Meyer Prof. Dr. Lutz Ackermann 《Angewandte Chemie (International ed. in English)》2018,57(9):2383-2387
Electrochemistry enabled C?H/N?H functionalizations at room temperature by external oxidant‐free cobalt catalysis. Thus, the sustainable cobalt electrocatalysis manifold proceeds with excellent levels of chemoselectivity and positional selectivity, and with ample scope, thus allowing electrochemical C?H activation under exceedingly mild reaction conditions at room temperature in water. 相似文献
16.
Wenling Li Christian Köhler Prof. Zhi Yang Prof. Dietmar Stalke Dr. Regine Herbst-Irmer Prof. Herbert W. Roesky 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(5):1193-1197
Lewis base cAACs stabilized monomeric silylenes with halogen or methyl substituents at the silicon center have not been reported due to the strong σ-donor and π-acceptor character of cAAC. To prepare these monomeric silylenes, we used the silicon(IV) precursors 5 and 6 with a nitrogen donor group L (L=o-C6H4NMe2). The cAAC-stabilized (cAAC=C(CH2)(CMe2)2N-Ar, Ar=2,6-iPr2C6H3) silylenes LSiCl(cAAC) ( 7 ) and LSiMe(cAAC) ( 8 ) were synthesized by reduction of LSiCl3 and LSiMeCl2 with two equivalents of KC8 in the presence of one equivalent of cAAC, respectively. Compounds 7 and 8 were characterized by single-crystal X-ray crystallography, NMR spectroscopy, and elemental analysis. Compounds 7 and 8 are stable in the solid state as well as in solution at room temperature for at least four months under inert conditions. 相似文献
17.
A ligand-free Pd-catalyzed cross-coupling of substituted allyl(trimethyl)silanes with aryl iodides enabled by silver salts was developed. This reaction delivered allylic arenes chemoselectively and regioselectively. The study suggested that the reaction might proceed through oxidative addition of ArI to Pd(0) followed by halide abstraction to give an electrophilic complex ArPdX, which further reacted with allyl(trimethyl)silanes via electrophilic addition/desilylation/reductive elimination to afford the allyl-aryl coupling products. 相似文献
18.
Synthesis of Stable Diarylpalladium(II) Complexes: Detailed Study of the Aryl–Aryl Bond‐Forming Reductive Elimination
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Tobias Gensch Dr. Nils Richter Gabriele Theumer Dr. Olga Kataeva Prof. Dr. Hans‐Joachim Knölker 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(32):11186-11190
The synthesis of diarylpalladium(II) complexes by twofold aryl C?H bond activation was developed. These intermediates of oxidative cyclization reactions are stabilized by chelation with acetyl groups while still maintaining sufficient reactivity to study their reductive elimination. Four distinct triggers were found for the reductive elimination of these complexes to dibenzofurans and carbazoles. Thermal elimination occurs at very high temperatures, whereas ligand‐promoted and oxidatively induced reductive eliminations proceed readily at room temperature. Under these conditions, no isomerization occurs. In contrast, weak Brønsted acids, such as acetic acid, lead to a sequence of proto‐demetalation, isomerization to a κ3‐diarylpalladium(II) complex, and reductive elimination to non‐symmetrical cyclization products. 相似文献
19.
Christian Däschlein Dr. Viktoria H. Gessner Dr. Carsten Strohmann Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(13):4048-4062
The direct α‐lithiation of methyl‐substituted silanes as an efficient method for the preparation and elaboration of Si‐chiral compounds is reported. Deprotonation of chiral oligosilanes occurs selectively and with high yields at the methyl group of the stereogenic silicon center, even in the presence of multiple methylsilyl or methylgermyl substituents. Computational studies have confirmed this preference as a consequence of pre‐coordination of the lithiating agent by the amino side‐arm and repulsion effects in the corresponding transition state. This complexation is also obvious from X‐ray structure analyses of the α‐lithiated silanes, which exhibit intriguing structure formation patterns differing in the type of aggregation and the amount of alkyllithium used. An alternative route to Si‐chiral compounds is also presented, which involves desymmetrization of dimethylsilanes mediated by a chiral side‐arm. Structure analyses and computational studies have shown that the diastereoselectivity of this α‐lithiation is influenced by the selectivity of the formation of the stereogenic nitrogen upon complexation of the alkyllithium. 相似文献
20.
Yusuke Iwama Dr. Kentaro Okano Dr. Kenji Sugimoto Prof. Dr. Hidetoshi Tokuyama 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(28):9325-9334
A racemic synthesis of mersicarpine ( 1 ) was achieved by the Mizoroki–Heck reaction and a DIBALH‐mediated reductive ring‐expansion reaction. Based on a first‐generation synthesis, a second‐generation enantiocontrolled total synthesis of (?)‐mersicarpine ( 1 ) was achieved by an 8‐pot/11‐step sequence in 21 % overall yield from commercially available 2‐ethylcyclohexanone. Subjection of a ketoester, which was prepared by an asymmetric Michael addition (according to the protocol by d’Angelo and Desmaële), and phenylhydrazine to modified Fischer indole conditions provided a six‐membered tricyclic indole. Benzylic oxidation and subsequent oxime formation provided a ketoxime, which was treated with diisobutylaluminum hydride (DIBALH) to construct the characteristic azepinoindole skeleton in good yield. In the DIBALH‐mediated reductive ring‐expansion reaction, gradually increasing the reaction temperature and in situ‐protection of the nitrogen in an oxygen‐sensitive azepinoindole with a benzyloxycarbonyl (Cbz) group were crucial for the high‐yielding process. With these methodologies, the short‐step and efficient synthesis of (?)‐mersicarpine was accomplished. Several synthetic efforts are also described. 相似文献