- Microwave-Assisted 1,3-Dioxa-[3,3]-Sigmatropic Rearrangement of Substituted Allylic Carbamates: Application to the Synthesis of Novel 1,3-Oxazine-2,4-dione Derivatives
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In a first instance, the effect of the microwave irradiation on the 1,3-Dioxa-[3,3]-sigmatropic rearrangement of aryl allylic carbamates was investigated. Under these new conditions, the reaction acceleration was clearly highlighted compared to convention
- Bou Zeid, Samar,Eid, Samar,Najjar, Fadia,Macé, Aurélie,Rivilla, Ivan,Cossío, Fernando P.,Dorcet, Vincent,Roisnel, Thierry,Carreaux, Fran?ois
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supporting information
(2021/11/22)
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- Palladium-Catalyzed Synthesis of α-Methyl Ketones from Allylic Alcohols and Methanol
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One-pot synthesis of α-methyl ketones starting from 1,3-diaryl propenols or 1-aryl propenols and methanol as a C1 source is demonstrated. This one-pot isomerization-methylation is catalyzed by commercially available Pd(OAc)2 with H2O as the only by-product. Mechanistic studies and deuterium labelling experiments indicate the involvement of isomerization of allyl alcohol followed by methylation through a hydrogen-borrowing pathway in these isomerization-methylation reactions.
- Biswal, Priyabrata,Samser, Shaikh,Meher, Sushanta Kumar,Chandrasekhar, Vadapalli,Venkatasubbaiah, Krishnan
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supporting information
p. 413 - 419
(2021/11/01)
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- Lanthanide-Catalyzed Tandem Addition of Amines to Cyanoalkenes: Synthesis of Cyclic Amidines
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A tandem insertion of aliphatic nitriles and unactivated alkenes to the N-H bond of secondary aliphatic amines catalyzed by simple trialkyl rare-earth metal complexes was disclosed. This reaction provides a highly atom-economic and stereoselective way to a range of cyclic amidines under mild reaction conditions.
- Hou, Jinsong,Yang, Gaosheng,Chai, Zhuo
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supporting information
p. 453 - 463
(2022/01/04)
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- Enantioselective Allylation of Alkenyl Boronates Promotes a 1,2-Metalate Rearrangement with 1,3-Diastereocontrol
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Alkenyl boronates add to Ir(π-allyl) intermediates with high enantioselectivity. A 1,2-metalate shift forms a second C-C bond and sets a 1,3-stereochemical relationship. The three-component coupling provides tertiary boronic esters that can undergo multiple additional functionalizations. An extension to trisubstituted olefins sets three contiguous stereocenters.
- Davis, Colton R.,Luvaga, Irungu K.,Ready, Joseph M.
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supporting information
p. 4921 - 4927
(2021/05/04)
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- Iridium-Catalyzed Asymmetric Allylic Alkylation of Deconjugated Butyrolactams
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Compared with the ever-growing list of nonprochiral nucleophiles in Ir-catalyzed asymmetric allylic substitution reactions, prochiral nucleophiles are less studied. We present a new prochiral nucleophile, namely, deconjugated butyrolactam, for Ir-catalyze
- Mitra, Sankash,Mukherjee, Santanu
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supporting information
p. 3021 - 3026
(2021/05/04)
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- Synthesis of C5-allylindoles through an iridium-catalyzed asymmetric allylic substitution/oxidation reaction sequence of N-alkyl indolines
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Iridium/Br?nsted acid cooperative catalyzed asymmetric allylic substitution reactions at the C5 position of indolines have been reported for the first time. The highly efficient protocol allows rapid access to various C5-allylated products in good to high
- Lu, Jiamin,Xu, Ruigang,Zeng, Haixia,Zhong, Guofu,Wang, Meifang,Ni, Zhigang,Zeng, Xiaofei
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supporting information
p. 3426 - 3431
(2021/05/07)
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- Pd-Catalyzed Asymmetric Acyl-Carbamoylation of an Alkene to Construct an α-Quaternary Chiral Cycloketone
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Herein, we report the palladium-catalyzed asymmetric acyl-carbamoylation of an alkene by employing thioesters as the acyl electrophiles and t-BuNC as the carbamoyl reagent, affording an α-quaternary chiral cycloketone in synthetically useful yields with excellent enantioselectivity. The reaction proceeded via asymmetric 1,2-migratory insertions of acyl-Pd into alkenes and subsequent migratory insertion of isocyanides into C(sp3)-PdII. The product could be diversified to some valuable skeletons with retention of enantiopurity, demonstrating the synthetic utility of this protocol.
- Liu, Min,Wang, Xing,Guo, Ziqiong,Li, Hanyuan,Huang, Wei,Xu, Hui,Dai, Hui-Xiong
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supporting information
p. 6299 - 6304
(2021/08/30)
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- [Pd]-Catalyzedpara-selective allylation of phenols: access to 4-[(E)-3-aryl/alkylprop-2-enyl]phenols
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4-[(E)-3-Arylprop-2-enyl]phenols are omnipresent scaffolds and constitute natural products and biologically significant compounds. Obtusastyrene and obtustyrene are two such phenolic-based natural products isolated fromDalbergia retusa. The development of strategies based on a site-selective allylation, particularly protecting group-free substrates and non-activated coupling agents, is indispensable in organic synthesis. Herein, we present a highly regioselective [Pd]-catalyzedpara-allylation of phenols using simple, inactivated allylic alcohols as allylating coupling partners. Notably, this strategy is successful in open-air and under mild reaction conditions. Besides, the efficacy of the present protocol was demonstrated by the direct synthesis of obtusastyrene and obtustyrene.
- Chinnabattigalla, Sreenivasulu,Choudhury, Aditya,Gedu, Satyanarayana
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supporting information
p. 8259 - 8263
(2021/10/12)
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- Nickel-Catalyzed Reductive Csp2-Csp3Cross Coupling Using Phosphonium Salts
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A nickel-catalyzed reductive cross coupling with phosphonium salts and allylic C(sp3)-O bond electrophiles, which granted direct construction of the C(sp2)-C(sp3) bond, is successfully developed. The protocol features broad substrate scope, high-functional-group tolerance, and heterocycle compatibility. Notably, the much more challenging reductive cross coupling with heterocyclic thiazolylphosphonium salts has also been accomplished for the first time.
- Liang, Hongze,Lu, Xinyao,Luo, Yunjie,Man, Xi,Mou, Zehuai,Wang, Huifei,Wang, Yuting,Yang, Mengwan
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supporting information
p. 8183 - 8188
(2021/11/13)
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- Highly efficient kinetic resolution of aryl-alkenyl alcohols by ru-catalyzed hydrogen transfer
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No matter through asymmetric reduction of ketones or kinetic resolution of secondary alcohols, enantioselective synthesis of the corresponding secondary alcohols is challenging when the two groups attached to the prochiral or chiral centers are spatially
- Jin, Ming Yu,Tao, Guanyu,Xing, Xiangyou,You, Yipeng
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supporting information
(2021/12/24)
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- Using Neighboring-Group Participation for Acyclic Stereocontrol in Diastereoselective Substitution Reactions of Acetals
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Neighboring-group participation of an ester enabled stereocontrol in substitution reactions of acyclic acetals. The ester group formed a trans-fused dioxolenium ion intermediate, which underwent a substitution reaction at the acetal carbon atom to afford the product with high diastereoselectivity. Neighboring-group participation was confirmed by isolating dioxolane products resulting from nucleophilic addition at C-2 of a 1,3-dioxolenium ion intermediate. Using a pivaloate ester as the participating group in combination with strong nucleophiles produced substitution products with diastereoselectivities of ≥90:10.
- Ramdular, Amanda,Woerpel, K. A.
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supporting information
(2020/06/08)
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- In Situ Ring-Closing Strategy for Direct Synthesis of N-Heterocyclic Carbene Nickel Complexes and Their Application in Coupling of Allylic Alcohols with Aryl Boronic Acids
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A in situ ring-closing strategy was developed for the synthesis of N-heterocyclic carbene nickel complexes. The process was carried out in air, and did not require solvent purification. The resulting nickel complexes were investigated as catalysts for the coupling of allylic alcohols with aryl boronic acids. A wide range of allylic substrates and aryl acids proved to be applicable to this catalytic system. Control experiments suggest that the Ni(0) may be the true active species in the coupling reactions. (Figure presented.).
- Wang, Yu-Bin,Liu, Bin-Yuan,Bu, Qingqing,Dai, Bin,Liu, Ning
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supporting information
p. 2930 - 2940
(2020/06/17)
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- Synthesis of 2-(3-Arylallylidene)-3-oxindoles via Dirhodium(II)-Catalyzed Reaction of 3-Diazoindolin-2-imines with 1-Aryl-Substituted Allylic Alcohols and Computational Insights
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A straightforward approach for the synthesis of 2-(3-arylallylidene)-3-oxindoles has been achieved by the dirhodium(II)-catalyzed reaction of 3-diazoindolin-2-imines with 1-aryl-substituted allylic alcohols. This protocol employs easily accessible feedsto
- Gao, Ke,Kou, Luyao,Fu, Rui,Bao, Xiaoguang
-
supporting information
p. 1292 - 1297
(2020/02/11)
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- Palladium-catalyzed regioselective synthesis of B(4,5)-or B(4)-substituted: O-carboranes containing α,β-unsaturated carbonyls
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With the help of a carboxylic acid directing group, Pd-catalyzed regioselective synthesis of B(4,5)-or B(4)-substituted o-carboranes containing α,β-unsaturated carbonyls has been reported. The-COOH, removed during the course of the reaction, is responsible for controlling the regioselectivity. The desired products could be obtained in moderate to good yields.
- Li, Jiaoyi,Lu, Jian,Tian, Song,Wang, Qian,Zhang, Chuyi,Zhang, Jianwei,Zhou, Ling
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supporting information
p. 4723 - 4727
(2020/07/13)
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- Highly Enantioselective Iridium-Catalyzed Coupling Reaction of Vinyl Azides and Racemic Allylic Carbonates
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The iridium-catalyzed enantioselective coupling reaction of vinyl azides and allylic electrophiles is presented and provides access to β-chiral carbonyl derivatives. Vinyl azides are used as acetamide enolate or acetonitrile carbanion surrogates, leading to γ,δ-unsaturated β-substituted amides as well as nitriles with excellent enantiomeric excess. These products are readily transformed into chiral N-containing building blocks and pharmaceuticals. A mechanism is proposed to rationalize the chemoselectivity of this coupling reaction.
- Han, Min,Yang, Min,Wu, Rui,Li, Yang,Jia, Tao,Gao, Yuanji,Ni, Hai-Liang,Hu, Ping,Wang, Bi-Qin,Cao, Peng
-
supporting information
p. 13398 - 13405
(2020/09/02)
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- Asymmetric Synthesis of γ-Secondary Amino Alcohols via a Borrowing-Hydrogen Cascade
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The borrowing-hydrogen (or hydrogen autotransfer) process, where the catalyst dehydrogenates a substrate and formally transfers the H atom to an unsaturated intermediate, is an atom-efficient and environmentally benign transformation. Described here is an example of an asymmetric borrowing-hydrogen cascade for the formal anti-Markovnikov hydroamination of allyl alcohols to synthesize optically enriched γ-secondary amino alcohols. By exploiting the Ru-(S)-iPrPyme catalyst with minimal stereogenicity, a cascade process including dehydrogenation, conjugate addition, and asymmetric reduction was developed. The mild conditions, functional group tolerance, and broad substrate scope (54 examples) demonstrate the synthetic practicality of the catalytic system.
- Chang, Xiaoyong,Chen, Fumin,He, Dongxu,Jin, Ming Yu,Pan, Yupeng,Xing, Xiangyou,You, Yipeng
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supporting information
p. 7278 - 7283
(2020/10/02)
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- A Construction of α-Alkenyl Lactones via Reduction Radical Cascade Reaction of Allyl Alcohols and Acetylenic Acids
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An iron-catalyzed cascade reaction of radical reduction of allyl alcohols and acetylenic acids to construct polysubstituted α-alkenyl lactones has been developed. In this paper, various allyl alcohols can form allyl ester intermediates and are further transformed into alkyl radicals, which form products through intramolecular reflex-Michael addition. In addition, this method can be used to prepare spirocycloalkenyl lactones. Interestingly, this protocol can be used to synthesize the skeleton structure of natural products. Moreover, the product can be further transformed into a β-methylene tetrahydrofuran and tetrahydrofuran diene.
- Zhang, Hua,Zhang, Guo-Min,He, Shuai,Shi, Zhi-Chuan,Zhang, Xiao-Mei,Wang, Ji-Yu
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supporting information
p. 8337 - 8344
(2020/11/03)
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- Size-Exclusion Borane-Catalyzed Domino 1,3-Allylic/Reductive Ireland–Claisen Rearrangements: Impact of the Electronic and Structural Parameters on the 1,3-Allylic Shift Aptitude
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The reductive Ireland–Claisen rearrangement through borane-mediated hydrosilylation is reported. The method employs a borane catalyst with a special structural design and affords access to synthetically relevant products with high diastereoselectivity. Depending on electronic and structural parameters, the reaction can be coupled with a 1,3-allylic shift, thus the valence isomer of the Ireland–Claisen product is formed.
- Fegyverneki, Dániel,Kolozsvári, Natália,Molnár, Dániel,Egyed, Orsolya,Holczbauer, Tamás,Soós, Tibor
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supporting information
p. 2179 - 2183
(2019/01/04)
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- Ruthenium-Catalyzed Redox Isomerizations inside Living Cells
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Tailored ruthenium(IV) complexes can catalyze the isomerization of allylic alcohols into saturated carbonyl derivatives under physiologically relevant conditions, and even inside living mammalian cells. The reaction, which involves ruthenium-hydride intermediates, is bioorthogonal and biocompatible, and can be used for the "in cellulo" generation of fluorescent and bioactive probes. Overall, our research reveals a novel metal-based tool for cellular intervention, and comes to further demonstrate the compatibility of organometallic mechanisms with the complex environment of cells.
- Vidal, Cristian,Tomás-Gamasa, María,Gutiérrez-González, Alejandro,Mascarenas, José L.
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supporting information
p. 5125 - 5129
(2019/03/29)
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- One-Pot Conversion of Allylic Alcohols to α-Methyl Ketones via Iron-Catalyzed Isomerization-Methylation
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A one-pot iron-catalyzed conversion of allylic alcohols to α-methyl ketones has been developed. This isomerization-methylation strategy utilized a (cyclopentadienone)iron(0) carbonyl complex as precatalyst and methanol as the C1 source. A diverse range of allylic alcohols undergoes isomerization-methylation to form α-methyl ketones in good isolated yields (up to 84% isolated yield).
- Latham, Daniel E.,Polidano, Kurt,Williams, Jonathan M. J.,Morrill, Louis C.
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supporting information
p. 7914 - 7918
(2019/10/16)
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- A Convenient Palladium-Catalyzed Carbonylative Synthesis of (E)-3-Benzylidenechroman-4-ones
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A convenient palladium-catalyzed carbonylation reaction for the efficient synthesis of (E)-3-benzylidenechroman-4-ones has been developed. Using TFBen as a solid CO source, a range of substituted (E)-3-benzylidenechroman-4-ones were prepared in moderate to good yields with 2-iodophenols and allyl chlorides as the substrates. Additionally, substituted quinolin-4(1H)-ones can also be obtained with 2-iodoaniline as the starting material.
- Wang, Wei-Feng,Peng, Jin-Bao,Qi, Xinxin,Ying, Jun,Wu, Xiao-Feng
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supporting information
p. 3521 - 3524
(2019/02/14)
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- Olefin Oxyamination with Unfunctionalized N-Alkylanilines
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N-Alkylanilines have rarely been used in oxyamination reactions, due to the normally necessary pre-functionalization of the N-atom. Also, the formation of aminium radical cations (ARCs) of anilines bearing alkyl substituents is plagued by the ARC's tendency to instantaneously convert to α-amino radicals or iminium ions. We present a readily available reagent combination that addresses both challenges, and thus allows for an oxyamination with N-alkylanilines via ARCs as the crucial reactive intermediates and excellent diastereoselectivity. (Figure presented.).
- Gao, Shuang,Niggemann, Meike
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supporting information
p. 1549 - 1553
(2019/02/09)
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- Intramolecular photocycloaddition reactions of 2- and 4-(5-arylpent-4-enyl)-1-cyanonaphthalenes
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Photoreactions of 1-cyanonaphthalene derivatives containing 5-arylpent-4-enyl groups at C-2 or C-4 of the naphthalene ring were investigated. Photoreactions of C-2 derivatives in benzene or CH3CN generated intramolecular [2 + 2] and [3 + 2] photocycloadducts. Substances bearing electron-rich and electron-poor phenyl groups produced respective [2 + 2] and [3 + 2] photocycloadducts preferentially. In contrast, photoreactions of C-4 linked 1-cyanonaphthalenes produced intramolecular [4 + 2] photocycloadducts as main products along with stereoisomers of tricyclic compounds as minor products. The formation of [4 + 2] photocycloadducts was promoted by using benzophenone or Michler's ketone triplet photosensitization, and quenched by O2 or ferrocene. Intramolecular singlet exciplexes, which serve as important intermediates in the mechanistic pathways for these reactions, governed the site-selectivities in photoreactions of both of the 2- and 4-(5-arylpent-4-enyl)-1-cyanonaphthalenes. In addition, [4 + 2] photocycloadducts were observed to undergo di-π-methane rearrangement under irradiation conditions to produce angular triquinane derivatives.
- Maeda, Hajime,Enya, Kouhei,Negoro, Naoki,Mizuno, Kazuhiko
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p. 173 - 184
(2019/02/15)
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- Oxazolinyl-Assisted Ru(II)-Catalyzed C-H Allylation with Allyl Alcohols and Synthesis of 4-Methyleneisochroman-1-ones
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We report herein a ruthenium-catalyzed, oxazoline-directed strategy for C-H allylation of aryl oxazolines using allylic alcohols as the coupling partner. The present transformation unravels the unusual reactivity of allylic alcohols in the synthesis of 4-
- Singh, Diksha,Kumar, Gangam Srikanth,Kapur, Manmohan
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p. 12881 - 12892
(2019/09/30)
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- Synthesis of Allylsilanes via Nickel-Catalyzed Cross-Coupling of Silicon Nucleophiles with Allyl Alcohols
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NiCl2(PMe3)2-catalyzed reaction of allyl alcohols with silylzinc reagents, including PhMe2SiZnCl, Ph2MeSiZnCl, and Ph3SiZnCl, was performed, achieving allylsilanes in high yields. Aryl- and heteroaryl-substituted allyl alcohols, (E)-3-arylprop-2-en-1-ols, 1-aryl-prop-2-en-1-ols, and (E)-1-phenylpent-1-en-3-ol can be employed in the transformation. A range of functional groups as well as heteroaryl groups were tolerated. Reaction exhibited high regioselectivity and E/Z-selectivity when 1- or 3-aryl-substituted allyl alcohols were used as the substrates. Reaction of chiral allyl alcohol, (S,E)-1-phenylpent-1-en-3-ol, yielded a configuration-inversion product (R,E)-dimethyl(phenyl)(1-phenylpent-1-en-3-yl)silane.
- Yang, Bo,Wang, Zhong-Xia
-
supporting information
p. 7965 - 7969
(2019/10/19)
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- Access to Saturated Thiocyano-Containing Azaheterocycles via Selenide-Catalyzed Regio-A nd Stereoselective Thiocyanoaminocyclization of Alkenes
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An efficient route for the synthesis of saturated thiocyano-containing azaheterocycles by selenide-catalyzed regio-A nd stereoselective thiocyanoaminocyclization of alkenes is disclosed. The desired products were obtained in moderate to high yields under mild conditions. The generality of this method was elucidated by its efficient application in thiocyano oxycyclization of alkenes.
- Wei, Wei,Liao, Lihao,Qin, Tian,Zhao, Xiaodan
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supporting information
p. 7846 - 7850
(2019/10/10)
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- Rh-Catalyzed Regioselective Dialkylation of Cage B-H bonds in o-Carboranes: Oxidative Heck Reactions via an Enol Isomerization
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In the presence of a carboxylic acid directing group, Rh-catalyzed regioselective directed dialkylation of B(4,5)-H bonds in o-carboranes and oxidative coupling with allylic alcohols is reported. This strategy constructs a series of 4,5-dialkylated o-carboranes in good yields with excellent regioselectivity. A possible catalytic cycle is proposed that involves a tandem sequence of Rh-catalyzed cage B-H activation, alkene insertion, selective β-H elimination, enol isomerization, and decarboxylation.
- Wang, Qian,Tian, Song,Zhang, Chuyi,Li, Jiangwei,Wang, Zhixuan,Du, Yongmei,Zhou, Ling,Lu, Jian
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supporting information
p. 8018 - 8021
(2019/10/19)
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- Catalytic Asymmetric Intramolecular Bromolactonization of α,β-Unsaturated Ketones
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Enantioselective bromolactonization by using an amino-urea catalyst to generate the important bromo-containing 3,4-dihydroisocoumarins is described. Excellent yields and good enantioselectivities could be achieved for various 3,4-dihydroisocoumarin compou
- Gan, Min,He, Hailong,Jiang, Xiaojian,Liu, Shenghui,Yi, Peng
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supporting information
p. 1474 - 1478
(2019/07/15)
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- A Ba/Pd Catalytic System Enables Dehydrative Cross-Coupling and Excellent E-Selective Wittig Reactions
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A Ba/Pd cooperative catalysis system was developed to enable the dehydrative cross-coupling of allylic alcohols with P-ylides to occur directly and promote a subsequent Wittig reaction in one pot. A variety of multisubstituted 1,4-dienes were isolated in good to excellent yields with broad P-ylides (stabilized by both ester and ketone carbonyl groups) and aldehyde (aliphatic and aromatic) substrates with excellent E selectivity.
- Xie, Peizhong,Fu, Weishan,Cai, Xinying,Sun, Zuolian,Wu, Ying,Li, Shuangshuang,Gao, Cuiqing,Yang, Xiaobo,Loh, Teck-Peng
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supporting information
p. 7055 - 7059
(2019/09/12)
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- Enantioselective addition of selenosulfonates to α,β-unsaturated ketones
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An organo-catalyzed enantioselective addition of selenosulfonates to α,β-unsaturated ketones was developed for the first time. With a chiral squaramide as an efficient catalyst, the desired α-selenylated ketones were obtained in a good yields with high enantioselectivity up to 89% ee, and good results could be obtained on a gram scale. The products could also be efficiently transformed into useful building blocks with a propenylic stereocenter; the strategy presented in this study may find further applications in organic synthesis.
- Luo, Shilong,Zhang, Nan,Wang, Zhen,Yan, Hailong
-
supporting information
p. 2893 - 2901
(2018/05/03)
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- Structural Modification of Natural Product Ganomycin i Leading to Discovery of a α-Glucosidase and HMG-CoA Reductase Dual Inhibitor Improving Obesity and Metabolic Dysfunction in Vivo
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It is a great challenge to develop drugs for treatment of metabolic syndrome. With ganomycin I as a leading compound, 14 meroterpene derivatives were synthesized and screened for their α-glucosidase and HMG-CoA reductase inhibitory activities. As a result, a α-glucosidase and HMG-CoA reductase dual inhibitor ((R,E)-5-(4-(tert-butyl)phenyl)-3-(4,8-dimethylnona-3,7-dien-1-yl)furan-2(5H)-one, 7d) with improved chemical stability and long-term safety was obtained. Compound 7d showed multiple and strong in vivo efficacies in reducing weight gain, lowering HbAlc level, and improving insulin resistance and lipid dysfunction in both ob/ob and diet-induced obesity (DIO) mice models. Compound 7d was also found to reduce hepatic steatosis in ob/ob model. 16S rRNA gene sequencing, SCFA, and intestinal mucosal barrier function analysis indicated that gut microbiota plays a central and causative role in mediating the multiple efficacies of 7d. Our results demonstrate that 7d is a promising drug candidate for metabolic syndrome.
- Wang, Kai,Bao, Li,Zhou, Nan,Zhang, Jinjin,Liao, Mingfang,Zheng, Zhongyong,Wang, Yujing,Liu, Chang,Wang, Jun,Wang, Lifeng,Wang, Wenzhao,Liu, Shuangjiang,Liu, Hongwei
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p. 3609 - 3625
(2018/05/01)
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- 1,3-Dioxa-[3,3]-sigmatropic Oxo-Rearrangement of Substituted Allylic Carbamates: Scope and Mechanistic Studies
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An unexpected 1,3-dioxa-[3,3]-sigmatropic rearrangement during the treatment of aryl- and alkenyl-substituted allylic alcohols with activated isocyanates is reported. The reorganization of bonds is highly dependent on the electron density of the aromatic
- Agirre, Maddalen,Henrion, Sylvain,Rivilla, Ivan,Miranda, José I.,Cossío, Fernando P.,Carboni, Bertrand,Villalgordo, José M.,Carreaux, Fran?ois
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p. 14861 - 14881
(2019/01/04)
-
- Ruthenium(II)-Catalyzed Regio- and Stereoselective C-H Allylation of Indoles with Allyl Alcohols
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A ruthenium-catalyzed C-H allylation of indoles with allyl alcohols via β-hydroxide elimination is reported. Without external oxidants and expensive additives, this reaction features mild reaction conditions, compatibility with various functional groups, and good to excellent regioselectivity and stereoselectivity.
- Wu, Xiaowei,Ji, Haitao
-
supporting information
p. 2224 - 2227
(2018/04/30)
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- Efficient Pd-Catalyzed Regio- and Stereoselective Carboxylation of Allylic Alcohols with Formic Acid
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Formic acid is efficiently used as a C1 source to directly carboxylate allylic alcohols in the presence of a low loading of palladium catalyst and acetic anhydride as additive to afford β,γ-unsaturated carboxylic acids with excellent chemo-, regio-, and stereoselectivity. The reaction proceeds through a carbonylation process with in situ-generated carbon monoxide under mild conditions, avoiding the use of high-pressure gaseous CO. A bisphosphine ligand with a large bite angle (4,5-bis{diphenylphosphino}-9,9-dimethylxanthene, Xantphos) was found to be uniquely effective for this transformation. The regio- and stereoconvergence of this reaction is ascribed to the thermodynamically favored isomerization of the allylic electrophile in the presence of the palladium catalyst.
- Fu, Ming-Chen,Shang, Rui,Cheng, Wan-Min,Fu, Yao
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supporting information
p. 8818 - 8822
(2017/07/11)
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- Superacid-Mediated Intramolecular Cyclization/Condensation: Facile One-Pot Synthesis of Spirotetracyclic Indanones and Indenes
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A facile, superacid-promoted, domino, one-pot synthesis of novel spirotetracyclic indanones through intramolecular Friedel-Crafts acylation/alkylation of α,β-unsaturated cinnamic acid esters is presented. Interestingly, when the β-aryl group contained ele
- Ramulu, Bokka Venkat,Kumar, Devarapalli Ravi,Satyanarayana, Gedu
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p. 2179 - 2183
(2017/09/26)
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- Regio- and enantioselective synthesis of chiral pyrimidine acyclic nucleosides via rhodium-catalyzed asymmetric allylation of pyrimidines
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A direct route to branched N-allylpyrimidine analogues is herein reported via the highly regio- and enantioselective asymmetric allylation of pyrimidines with racemic allylic carbonates. With [Rh(COD)Cl]2/chiral diphosphine as the catalyst, a r
- Liang, Lei,Xie, Ming-Sheng,Qin, Tao,Zhu, Man,Qu, Gui-Rong,Guo, Ha-Ming
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supporting information
p. 5212 - 5215
(2017/11/06)
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- Rhodium-Catalyzed Asymmetric N?H Functionalization of Quinazolinones with Allenes and Allylic Carbonates: The First Enantioselective Formal Total Synthesis of (?)-Chaetominine
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An unprecedented asymmetric N?H functionalization of quinazolinones with allenes and allylic carbonates was successfully achieved by rhodium catalysis with the assistance of chiral bidentate diphosphine ligands. The high efficiency and practicality of this method was demonstrated by a low catalyst loading of 1 mol % as well as excellent chemo-, regio-, and enantioselectivities with broad functional group compatibility. Furthermore, this newly developed strategy was applied as key step in the first enantioselective formal total synthesis of (?)-chaetominine.
- Zhou, Yirong,Breit, Bernhard
-
supporting information
p. 18156 - 18160
(2017/12/13)
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- Expanding the scope of the Babler–Dauben oxidation: 1,3-oxidative transposition of secondary allylic alcohols
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We report the catalytic chromium-mediated oxidation of secondary allylic alcohols to give α,β-unsaturated aldehydes with exclusive (E)-stereoselectivity. This facile procedure employs catalytic PCC (5?mol?%) and periodic acid (H5IO6) as a co-oxidant. This transformation occurs specifically with aromatic substituted allyl alcohols containing both electron withdrawing and electron donating substituents as well as a range of functional groups.
- Killoran, Patrick M.,Rossington, Steven B.,Wilkinson, James A.,Hadfield, John A.
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supporting information
p. 3954 - 3957
(2016/08/09)
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- Development of a Palladium-Catalyzed Carbonylative Coupling Strategy to 1,4-Diketones
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We report on a three-component palladium-catalyzed coupling strategy for accessing a wide range of 1,4-diketones, which represent important precursors to heterocycles. Our method relies on a carbonylative Heck reaction employing substituted allylic alcohols, aryl iodides, and carbon monoxide. The reaction conditions are mild and do not require high CO pressure, and a wide functional group tolerance is revealed, providing the desired 1,4-diketones in moderate to good yields. Furthermore, the methodology is adaptable to the selective installment of 13C-carbon isotopes at either one or both of the carbonyl positions.
- Yin, Hongfei,Nielsen, Dennis U.,Johansen, Mette K.,Lindhardt, Anders T.,Skrydstrup, Troels
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p. 2982 - 2987
(2016/07/06)
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- Titanocene(III) chloride mediated radical induced addition-elimination route to the synthesis of racemic and optically active trisubstituted tetrahydrofurans: Formal synthesis of magnofargesin and 7’-epimagnofargesin
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Titanocene(III) Chloride mediated radical induced synthesis of 4-benzylidene substituted tetrahydrofuran, a typical lignan skeleton, has been accomplished in good yield through addition-elimination route in racemic as well as in optically active forms. The method has been applied to the synthesis of furano lignans, magnofargesin (1) and 7’-epimagnofargesin (2) in optically active forms.
- Chakraborty,Mandal,Roy
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p. 1067 - 1079
(2016/07/19)
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- Improvements and Applications of the Transition Metal-Free Asymmetric Allylic Alkylation using Grignard Reagents and Magnesium Alanates
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Two new N-heterocyclic carbene (NHC) ligands have been synthesized and employed in the transition metal-free asymmetric allylic alkylation (AAA) mediated by Grignard reagents and magnesium alanates. The employment of these ligands showed high yields and improved regio- and enantioselectivity in the formation of tertiary and quaternary stereocenters. Moreover, the low catalyst loading (up to 0.3 mol%) and high scalability (up to 10 mmol) of this improved methodology provide a convenient access to biologically active compounds and synthetically valuable intermediates.
- Grassi, David,Alexakis, Alexandre
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supporting information
p. 3171 - 3186
(2015/11/03)
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- Organoselenium-catalyzed, hydroxy-controlled regio- and stereoselective amination of terminal alkenes: Efficient synthesis of 3-amino allylic alcohols
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An efficient route to prepare 3-amino allylic alcohols in excellent regio- and stereoselectivity in the presence of bases by orangoselenium catalysis has been developed. In the absence of bases α,β-unsaturated aldehydes were formed in up to 97% yield. Control experiments reveal that the hydroxy group is crucial for the direct amination.
- Deng, Zhimin,Wei, Jialiang,Liao, Lihao,Huang, Haiyan,Zhao, Xiaodan
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supporting information
p. 1834 - 1837
(2015/04/27)
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- Transition-Metal-Free Self-Hydrogen-Transferring Allylic Isomerization
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Phenanthroline and tert-butoxide have been established as powerful radical initiators in reactions such as the SRN1-type coupling reactions due to the cooperation of large heteroarenes and a special feature of tert-butoxide. The first phenanthroline-tert-butoxide-catalyzed transition-metal-free allylic isomerization is described. The resulting ketones are key intermediates for indenes. The control experiments rule out the base-promoted allylic anion pathway. The radical pathway is supported by experimental evidence that includes kinetic study, kinetic isotope effect, isotope-labeling experiments, trapping experiments, and EPR experiments.
- Zheng, Hong-Xing,Xiao, Zu-Feng,Yao, Chuan-Zhi,Li, Qiang-Qiang,Ning, Xiao-Shan,Kang, Yan-Biao,Tang, Yong
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supporting information
p. 6102 - 6105
(2016/01/09)
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- Synthesis of Quinolines from Allylic Alcohols via Iridium-Catalyzed Tandem Isomerization/Cyclization Combined with Potassium Hydroxide
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A new tandem catalytic process has been established for the synthesis of quinolines. This process utilizes the [IrCp?Cl2]2/KOH catalyzed isomerization/cyclization of allylic alcohols with 2-aminobenzyl alcohol. Both the secondary and primary allylic alcohols were investigated in this catalytic system to afford different substituted quinoline derivatives in moderate to good yields. A mechanism study showed the reaction following a tandem process integrating isomerization of allylic alcohols and oxidative cyclization of 2-aminobenzyl alcohol.
- Chen, Shu-Jie,Lu, Guo-Ping,Cai, Chun
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p. 976 - 984
(2015/03/30)
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- Asymmetric transfer hydrogenation of secondary allylic alcohols
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Racemic secondary allylic alcohols were transformed into optically active secondary alcohols by a combined Rucatalyzed isomerization/asymmetric transfer-hydrogenation reaction. The catalyst was generated in situ in isopropyl alcohol from di-μ-chlorobis[(p-cymene)chlororuthenium(II)], the chiral ligand (1S,2S)-N-(p-tolylsulfonyl)-1,2-diphenylethylenediamine, and K2CO3, and the products were afforded in yields up to 97% with up to 93% enantiomeric excess without the use of hydrogen gas. A Hammett study revealed that the reaction rate was enhanced with electronwithdrawing aryl substituents. The reaction supports the recent work published by Adolfsson et al. as new methodology for the synthesis of chiral compounds from allylic alcohols.
- Shoola, Christopher O.,DelMastro, Thomas,Wu, Ruoqiu,Sowa, John R.
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supporting information
p. 1670 - 1673
(2015/05/27)
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- Titanocene(III) chloride mediated radical-induced opening of monosubstituted epoxy acetates for the synthesis of primary allylic alcohols
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A simple and efficient method for the synthesis of primary allylic alcohols from monosubstituted epoxy acetates has been developed using titanocene(III) chloride mediated epoxide ring opening via acetate elimination.
- Chakraborty,Mandal,Roy
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p. 893 - 901
(2015/08/18)
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- Iridium-catalyzed enantioselective allylation of silyl enol ethers derived from ketones and α,β-unsaturated ketones
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The unified Ir-catalyzed enantioselective allylic substitution reactions of silyl enol ethers derived from ketones and α,β-unsaturated ketones with branched, racemic allylic alcohols are described. This transformation is catalyzed by the Carreira system and proceeds without fluoride, and with high ee and b:l ratio. The synthetic utility of this method was illustrated by the concise enantioselective total synthesis of marine natural products calyxolane A, B and by the assignment of the absolute configuration of calyxolane A.
- Liang, Xiao,Wei, Kun,Yang, Yu-Rong
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supporting information
p. 17471 - 17474
(2015/12/09)
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- 1,4-Diazabicyclo[2.2.2]octane-Promoted Aminotrifluoromethylthiolation of α,β-Unsaturated Carbonyl Compounds: N-Trifluoromethylthio-4-nitrophthalimide Acts as Both the Nitrogen and SCF3 Sources
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A novel difunctionalization reaction is described. It uses N-trifluoromethylthio-4-nitrophthalimide as the reagent, which serves as both the nitrogen and SCF3 sources. In the presence of DABCO (1,4-diazabicyclo[2.2.2]octane), the nitrogen and SCF3 groups can be incorporated into α,β-unsaturated carbonyl compounds easily and give versatile β-amino ketones and esters in good yields. This difunctionalization reaction features mild reaction conditions, high atom-economy, and efficient access to α-SCF3 amino acids.
- Xiao, Qing,He, Qijie,Li, Juncheng,Wang, Jun
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supporting information
p. 6090 - 6093
(2016/01/09)
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- Iridium-catalyzed C-3 allylation of indoles with allylic alcohols promoted by a bronsted acid
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A highly regioselective method has been developed for the allylation of indoles with an iridium catalyst. This regioselective procedure uses allylic alcohols directly as allylating agents in the presence of a catalytic amount of sulfuric acid. A wide rang
- Chen, Shu-Jie,Lu, Guo-Ping,Cai, Chun
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supporting information
p. 1717 - 1724
(2014/07/08)
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- N-Heterocyclic carbene-catalyzed double acylation of enones with benzils
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Thiazolium carbene-catalyzed reaction of aromatic 1,2-diketones with enones in aprotic solvents gave double acylation products in good yields, whereas hydroacylation products formed by Stetter reaction were not detected at all. These results suggested the generation of aroyloxyenamine species from the 1,2-diketones instead of hydroxyenamines (Breslow intermediates). This journal is
- Takaki, Ken,Ohno, Akira,Hino, Makoto,Shitaoka, Takashi,Komeyama, Kimihiro,Yoshida, Hiroto
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supporting information
p. 12285 - 12288
(2014/12/11)
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