- Synthesis of Indanones and Spiroindanones by Diastereoselective Annulation Based on a Hydrogen Autotransfer Strategy
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An unprecedented nickel-catalyzed domino reductive cyclization of alkynes and o-bromoaryl aldehydes is described. The reaction features broad substrate scope and is tolerant of a variety of functional groups, providing straightforward access to biologically significant indanones and spiroindanone pyrrolidine derivatives in good yields with excellent regio- and diastereoselectivity. Preliminary mechanistic studies have shown that indanones are formed by the cyclization of o-bromoaryl aldehydes and alkynes to form indenol intermediates, followed by hydrogen autotransfer.
- Chen, Yate,Ding, Zhengtian,Wang, Yiming,Liu, Wenfeng,Kong, Wangqing
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supporting information
p. 5273 - 5278
(2021/02/03)
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- Construction of Halofunctionalized Indenes via a Cascade Prins-Nazarov Cyclization Promoted by Dual Roles of BX3
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Halofunctionalization of various unactivated arylalkynes to the corresponding 1H-indenes in the presence of a particular class of carboxaldehydes and boron trihalides (BX3, X=F, Cl, Br, I) is described. A diverse array of halofunctionalized indenes substituted with a heterocycle has been synthesized regioselectively with BX3 as a promotor for the carbocyclization and a source of X? for halogenation. This reaction proceeds via a formal halogenative [4+1] cycloaddition between arylalkynes and carboxaldehydes promoted by boron trihalides to generate halofunctionalized indenes. The usefulness of the halofunctionalized indenes was demonstrated by their conversion to other derivatives via coupling, nucleophilic substitution, and oxidation. (Figure presented.).
- Lee, Yong Rok,Sultana, Sabera
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p. 927 - 941
(2020/01/25)
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- Bidentate NHC-Cobalt Catalysts for the Hydrogenation of Hindered Alkenes
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Herein, we report a series of easily accessible bidentate N-heterocyclic carbene (NHC) cobalt catalysts, which enable the hydrogenation of hindered alkenes under mild conditions. The four-coordinated bidentate NHC-Co(II) complexes were characterized by X-ray diffraction, elemental analysis, ESI-HRMS, and magnetic moment measurements, revealing a distorted-tetrahedral geometry and a high-spin configuration of the metal center. The activity of the in situ formed catalytic system, which was obtained from easily available NHC precursors, CoCl2, and NaHBEt3, was identical with those of well-defined NHC-cobalt catalysts. This highlights the potential utility of this reaction system.
- Wei, Zeyuan,Wang, Yujie,Li, Yibiao,Ferraccioli, Raffaella,Liu, Qiang
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p. 3082 - 3087
(2020/10/02)
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- Selective Divergent Synthesis of Indanols, Indanones, and Indenes via Acid-Mediated Cyclization of (Z)- and (E)-(2-Stilbenyl)methanols and Its Application for the Synthesis of Paucifloral F Derivatives
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Starting from bromo/iodobenzaldehyde derivatives, the corresponding (Z)- and (E)-(2-stilbenyl)methanols could be prepared in 2-5 steps via Pd-catalyzed cross-coupling reactions (Sonogashira and Heck reactions) followed by aryllithium/aryl Grignard addition. For the (E)-stilbenes, subsequent acid-mediated cyclization using p-TsOH immobilized on silica (PTS-Si) at low temperatures furnished the 2,3-trans-1-indanols with complete stereocontrol at the C2-C3. Further oxidization of the alcohol provided the indanones, which are structurally related to the natural product paucifloral F. At higher temperatures, 1,2- and 2,3-disubstituted indenes could be selectively prepared in good to excellent yields. On the other hand, the (Z)-stilbenes, under similar conditions (PTS-Si), did not give the indanols; only the 1,2-disubstituted indenes could be obtained. To gain further insights into the stereochemistry at C2-C3 for the (Z)-stilbenes, hydride or azide was employed as a nucleophile; the corresponding indane products were obtained with the cis stereochemistry at the C2-C3. Thus, the (Z)- or (E)-olefin geometry of the substrate directed the stereoselective indanyl cyclization to furnish the cis or trans at the C2-C3 ring junction, respectively, while reaction conditions controlled the selectivity of the product types.
- Jongcharoenkamol, Jira,Chuathong, Patsapon,Amako, Yuka,Kono, Masato,Poonswat, Kasam,Ruchirawat, Somsak,Ploypradith, Poonsakdi
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p. 13184 - 13210
(2018/11/02)
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- Preparation method of 3-aryl-1-indanone derivate
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The invention discloses a preparation method of a 3-aryl-1-indanone derivate. The structural formula of the 3-aryl-1-indanone derivate is shown in the formula III. The preparation method comprises the following steps that a compound shown in the formula I reacts with a compound shown in the formula II in the presence of methyl trifluoromethanesulfonate, and therefore the 3-aryl-1-indanone derivate shown in the formula III is obtained. The preparation method of the 3-aryl-1-indanone derivate is scientific and reasonable, 3-aryl-1-indanone derivates with various substituent groups can be obtained, the raw materials are easy to obtain, no metal participates in the reaction, reaction atoms are economical, and meanwhile the preparation method has the advantages that operation is simple and convenient, the synthesis productive rate is high, the product is easy to purify, and environmental protection is achieved.
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Paragraph 0022; 0023; 0024; 0025; 0026
(2016/10/17)
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- Palladium-catalyzed asymmetric reductive Heck reaction of aryl halides
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Asymmetric reductive Heck reaction of aryl halides is realized in high stereoselectivity. Hydrogen-bond donors, trialkylammonium salts in a glycol solvent, were used to promote halide dissociation from neutral arylpalladium complexes to access cationic, stereoselective pathways.
- Yue, Guizhou,Lei, Kaining,Hirao, Hajime,Zhou, Jianrong
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p. 6531 - 6535
(2015/06/08)
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- Stereoselective palladium-catalyzed α-arylation of 3-aryl-1-indanones: An asymmetric synthesis of (+)-pauciflorol F
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Highly stereoselective, palladium-catalyzed α-arylation reactions of 3-aryl-1-indanones with aryl bromides are described. The use of sodium tert-butoxide as a base in this process is required to elevate the efficiencies and stereoselectivities of these re
- Lee, Bong Hyang,Choi, Young Lok,Shin, Seunghoon,Heo, Jung-Nyoung
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experimental part
p. 6611 - 6618
(2011/10/02)
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- Novel one-pot approach to synthesis of indanones Through Sb(V)-catalyzed reaction of phenylalkynes with aldehydes
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Catalytic SbF5 and the use of EtOH as an additive efficiently converted a mixture of phenylalkynes and aldehydes to indanone compounds in one pot, and the reaction stereoselectively afforded the corresponding 2,3-disubstituted indanones as a single trans-isomer.
- Saito, Akio,Umakoshi, Masaharu,Yagyu, Naomi,Hanzawa, Yuji
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supporting information; experimental part
p. 1783 - 1785
(2009/04/10)
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- Toward the synthesis of caraphenol C: Substituent effect on the Nazarov cyclization of 2-arylchalcones
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A mild and versatile synthesis of cis-2,3-diarylindanones using a Nazarov cyclization strategy was reported. The substituent effect on the stereochemistry of the cyclization was discussed. Georg Thieme Verlag Stuttgart.
- Zhu, Jun,Zhong, Chen,Lu, Hong-Fu,Li, Guang-Yu,Sun, Xun
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p. 458 - 462
(2008/04/01)
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- Synthesis of α,β-unsaturated ketones by rhodium-catalyzed carbonylative arylation of internal alkynes with arylboronic acids
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The Rh-catalyzed reaction of arylboronic acids with internal alkynes under a CO atmosphere in the presence of an acid additive afforded α,β-unsaturated ketones as the major products. Hydroacylation of internal alkynes, except in the case of diaryl acetylenes, proceeded in syn fashion, yielding the E-configured isomer. A mixture of E- and Z-isomers was obtained with diphenyl acetylene. Reactions were also highly regioselective for various nonsymmetric alkynes.
- Ku?, Melih,Artok, ?zge Aksin,Ziyanak, Firat,Artok, Levent
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experimental part
p. 2587 - 2592
(2009/04/16)
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- Rhodium-catalyzed carbonylative arylation of alkynes with arylboronic acids: An efficient and straightforward method in the synthesis of 5-aryl-2(5H)-furanones
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5-Aryl-2(5H)-furanones can be synthesized by the Rh-catalyzed reactions of arylboronic acids with internal alkynes under a CO atmosphere. The Royal Society of Chemistry 2006.
- Aksin, Oezge,Dege, Nurcan,Artok, Levent,Tuerkmen, Hayati,Cetinkaya, Bekir
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p. 3187 - 3189
(2008/09/19)
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- Reaction of aminocarbene complexes of chromium with alkynes 10. From large to small cyclic amines: Single versus double alkyne insertions
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For the purpose of comparing the reaction of various aminocarbene complexes of chromium with alkynes and to ascertain several points of the mechanism of their interaction, a series of complexes derived from large cyclic amines, HN(CH2)n (n≥6) and from a small cyclic amine (n=2) was synthesized. In the case of the larger amines, all the complexes examined herein, led to the expected bridgehead lactams 12 as the major product, providing strong evidence for a concerted rearrangement of an intermediate nitrogen-ylid complex such as 4. The X-ray structure of the lactam complex 12d (n=12) has been established in order to confirm the ring opening and the migration of the twelve carbon-atom alkyl chain from nitrogen to the γ-carbon. Interestingly, the last possibility, the migration from nitrogen to oxygen in 4, which had so far not been observed but which according to calculations should also be possible, took place in the case of complex 10b (n=7), giving rise, yet in low yield, to an alkoxypyrrole 14. Minor products resulting from annulation reactions without CO insertions, were also observed. For aminocarbene complexes derived from methylaziridine (n=2), important results, which substantiate previous observations, have been obtained especially as far as the mechanism of the insertion reaction is concerned: the regioselectivity of the ring-opening reaction could be established by X-ray crystallography on two isomeric complexes 25 and 26, the timing of the various steps could be determined by the examination of the reactivity of vinyl-aziridinyl carbene complexes 31 and 35 which led surprisingly to aziridinyl phenols 33 and 36. Finally, an unexpected product, the structure of which could also be established by X-ray crystallography as 27, and resulting from the oxidation at the α position of the carbonyl in complexes 25 or 26 was isolated during the interaction of complex 23 with diphenylacetylene.
- Lafollee-Bezzenine, Sophie,Parlier, Andree,Rudler, Henri,Vaissermann, Jacqueline,Daran, Jean-Claude
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- Synthesis of diastereoisomeric 1,2,3-triphenylindans
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The stereoisomers of 1,2,3-triphenylindans were synthesized via 1,2,3-triphenylindan-1-ols. The configurational assignments of all the compounds were made by chemical and spectroscopic methods. An unexpected compound was isolated as a by-product of the Gr
- Alesso, Elba N.,Finkielsztein, Liliana M.,Lantano, Beatriz,Bianchi, Daniel E.,Moltrasio Iglesias, Graciela Y.,Aguirre, Jose M.
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p. 149 - 152
(2007/10/03)
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- The Friedel-Crafts arylation of α-substituted chalcones revisited: Highly stereospecific synthesis of trans-2,3-diphenyl-indan-1-one derivatives
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The Lewis or protic acid promoted cycloisomerization of 1,2,3-triphenylpropenone in nitroethane as solvent has given trans-2,3-diphenyl-indan-1-one with complete diastereoselection in good to excellent chemical yield.
- Marco, Jose L.
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p. 4225 - 4231
(2007/10/03)
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- Generation and Trapping of Cyclopropenes from 2-Alkoxy-1,1-dichlorocyclopropanes
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In presence of crown ether, 2-alkoxy-1,1-dichlorocyclopropanes react with t-BuOK/THF preferentially via ring opening to 2-chloroalk-2-en-1-ones and alkynones or to chlorocyclopropenes.The latter may be intercepted with 1,3-diphenylisobenzofuran, but in th
- Mueller, Paul,Pautex, Nicole
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- SYNTHESIS OF INDENES FROM ALKYNES AND PHENYL AMINO CHROMIUM CARBENE COMPLEXES
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Reactions of phenyl morpholino or pyrrolidino chromium carbene complexes with alkynes in DMF at 120-125 grad C resulted in exclusive formation of the indene derivatives.
- Yamashita, A.
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p. 5915 - 5918
(2007/10/02)
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- Reaktionen mit Radikalanionen, IV. Synthese von Mono- und Diketonen aus Carboxyl- und α,β-ungesaettigten Carbonyl-Verbindungen
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1,2-Diketones of the benzil type were obtained in the reaction of aromatic carboxylic compounds with lithium naphthalenide.The scope of this reaction was investigated. α,β-Unsaturated ketones yielded hydrodimerisation, hydrogenation and hydroxylation products.
- Kirrstetter, Reiner G. H.,Vagt, Uwe
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p. 630 - 637
(2007/10/02)
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- A Comparative Study of the Reactions of Phthalides, Naphthalides and Related Compounds
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Synthesis of thiobenzalnaphthalide (II) and 2-substituted-3-benzylidene-2,3-dihydrobenzisoquinolin-1(2H)-ones (IV) is described. 2-Phenylphenalene-1,3(2H)-dione (V) on halogenation gives 2-halo-2-phenylphenalene-1,3(2H)-diones(VI) which react with am
- El-Sharief, A. M. Sh.,Hammad, N. I. S.,Mohamed, Y. A.
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p. 456 - 459
(2007/10/02)
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