- Palladium-Catalyzed Modular and Enantioselective cis-Difunctionalization of 1,3-Enynes with Imines and Boronic Reagents
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Here we report that a palladium(0) complex can mediate the unprecedented intermolecular coupling reaction of 1,3-enynes and N-sulfonylimines regio- and stereoselectively, and the resultant palladium(II) species undergo a cascade Suzuki reaction with organ
- He, Qing,Zhu, Lei,Yang, Zhen-Hong,Zhu, Bo,Ouyang, Qin,Du, Wei,Chen, Ying-Chun
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supporting information
p. 17989 - 17994
(2021/11/10)
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- Gold catalyzed efficient preparation of dihydrobenzofuran from 1,3-enyne and phenol
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A gold catalyzed formal intermolecular [2+3] cyclo-coupling of 1,3-enynes with phenols was developed to prepare dihydrobenzofuran derivatives with the addition of 2,6-dichloropyridine N-oxide, in which, a highly ortho-selective phenol SEAr functionalizati
- Wang, Yu-Jiang,Zhang, Yuan,Qiang, Zou,Liang, Jia-Ying,Chen, Zili
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supporting information
p. 12607 - 12610
(2021/12/07)
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- Regioselective Access to 3-Ethylideneflavanones via Rhodium(I)-Catalyzed 1,3-Enyne Hydroacylation/Annulation Cascades
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The highly efficient synthesis of 3-ethylideneflavanones through sequential rhodium(I)-catalyzed hydroacylation of terminal aryl-substituted 1,3-enynes with chelating aldehydes and annulation is described. This straightforward protocol highlights an unprecedented C3-regioselective hydroacylation of 1,3-enynes, excellent functional group compatibility, and complete atom economy. (Figure presented.).
- Chang, Zhi-Xin,Li, Fu-Rong,Xia, Chengcai,Li, Fei,Li, Hong-Shuang
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supporting information
p. 1722 - 1726
(2021/02/20)
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- Direct access to pentenedinitriles: Via Ni-catalyzed dihydrocyanation of 1,3-enynes
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A highly regio-and stereoselective dihydrocyanation of 1,3-enynes was implemented by nickel/diphosphine catalysts. This reaction represents the first example of Ni-catalyzed dihydrocyanation of 1,3-enynes using TMSCN and MeOH as HCN surrogates. In this tr
- Fang, Xianjie,Gao, Jihui,Sun, Feilong
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supporting information
p. 6858 - 6861
(2020/07/04)
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- Preparation of Chiral Allenes through Pd-Catalyzed Intermolecular Hydroamination of Conjugated Enynes: Enantioselective Synthesis Enabled by Catalyst Design
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In this study, we establish that conjugated enynes undergo selective 1,4-hydroamination under Pd catalysis to deliver chiral allenes with pendant allylic amines. Several primary and secondary aliphatic and aryl-substituted amines couple with a wide range of mono- and disubstituted enynes in a nonenantioselective reaction where DPEphos serves as the ligand for Pd. Benzophenone imine acts as an ammonia surrogate to afford primary amines in a two-step/one-pot process. Examination of chiral catalysts revealed a high degree of reversibility in the C-N bond formation that negatively impacted enantioselectivity. Consequently, an electron-poor ferrocenyl-PHOX ligand was developed to enable efficient and enantioselective enyne hydroamination.
- Adamson, Nathan J.,Jeddi, Haleh,Malcolmson, Steven J.
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supporting information
p. 8574 - 8583
(2019/06/04)
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- Catalytic Regio- and Enantioselective Proton Migration from Skipped Enynes to Allenes
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Chiral allenes are highly valuable as versatile synthetic intermediates and core skeletons of various functional organic molecules. Despite marked recent advances, the straightforward catalytic enantioselective synthesis of hydrocarbon allenes from readil
- Wei, Xiao-Feng,Wakaki, Takayuki,Itoh, Taisuke,Li, Hong-Liang,Yoshimura, Takayoshi,Miyazaki, Aya,Oisaki, Kounosuke,Hatanaka, Miho,Shimizu, Yohei,Kanai, Motomu
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p. 585 - 599
(2019/03/11)
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- Triple-Bond Insertion Triggers Highly Regioselective 1,4-Aminomethylamination of 1,3-Enynes with Aminals Enabled by Pd-Catalyzed C-N Bond Activation
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A highly chemo- and regioselective 1,4-aminomethylamination of simple enynes with aminals to allenic 1,5-diamines by taking advantage of C-N bond activation has been reported. The reaction proceeds under mild reaction conditions and can be performed under
- Zhang, Yanchen,Yu, Bangkui,Gao, Binjian,Zhang, Tianze,Huang, Hanmin
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supporting information
(2019/01/21)
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- Triple-Bond Insertion Triggers Highly Regioselective 1,4-Aminomethylamination of 1,3-Enynes with Aminals Enabled by Pd-Catalyzed C-N Bond Activation
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A highly chemo- and regioselective 1,4-aminomethylamination of simple enynes with aminals to allenic 1,5-diamines by taking advantage of C-N bond activation has been reported. The reaction proceeds under mild reaction conditions and can be performed under
- Zhang, Yanchen,Yu, Bangkui,Gao, Binjian,Zhang, Tianze,Huang, Hanmin
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supporting information
p. 535 - 539
(2019/01/24)
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- Intermolecular [3+2] Annulation of Cyclopropylanilines with Alkynes, Enynes, and Diynes via Visible Light Photocatalysis
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One-step syntheses of carbocycles substituted with amines from simple starting materials remain rare. We recently developed an intermolecular [3+2] annulation of cyclopropylanilines with alkenes and alkynes that enables this one-step synthesis. Herein, we
- Nguyen, Theresa H.,Morris, Scott A.,Zheng, Nan
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supporting information
p. 2831 - 2837
(2016/02/18)
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- Arylsulfonylacetylenes as alkynylating reagents
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The unexpected anti-Michael addition of RLi to β-substituted sulfonylacetylenes, followed by in situ elimination of the ion sulfinate, allows the alkynylation of C(sp2) and C(sp3). Aryl and heteroaryl acetylenes, enynes, and mono and dialkyl alkynes can be obtained in very high yields under very mild conditions, avoiding the use of transition metals as catalysts and, in many cases, haloderivatives as starting materials. Furthermore, the use of lithium 2-p-tolylsulfinyl benzylcarbanions as nucleophiles of these reactions allows their stereocontrolled alkynylation, affording enantiomerically pure alkynes or enantioenriched allenes depending on the protonating agent (NH4Cl or H2O).
- Marzo, Leyre,Aleman, Jose,Garcia Ruano, Jose Luis
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p. 403 - 407
(2013/07/26)
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- Tunable cross coupling of silanols: Selective synthesis of heavily substituted allenes and butadienes
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1,3-Dienyl-2-silanols with a wide range of substitution patterns are readily obtained by palladium-catalyzed silaboration of 1,3-enynes followed by Suzuki-Miyaura cross coupling with aryl bromides. Subsequent Hiyama-Denmark cross coupling with aryl iodides provides either 1,3- or 1,2-dienes in high yields. The site selectivity can be fully controlled by the choice of activator used in the coupling reaction. In the presence of strong bases such as NaOt-Bu, KOt-Bu, and NaH, clean formation of 1,2-dienes takes place via allylic rearrangement. In contrast, stereo- and site-selective formation of tetra- and trisubstituted 1,3-dienes results from use of Ag2O and Bu 4NF·3H2O, respectively, as activators. Under microwave heating at 100 °C the base-mediated cross couplings are largely accelerated and are completed within one hour or less. The ratio of diastereomeric allenes varies depending on the substitution pattern of the silanol and ranges from >99:1 to 52:48.
- Zhou, Hui,Moberg, Christina
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supporting information
p. 15992 - 15999
(2012/11/07)
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- Beyond the limits: Palladium-N-heterocyclic carbene-based catalytic system enables highly efficient [4+2] benzannulation reactions
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A highly efficient catalytic system for the palladium-catalyzed [4+2] benzannulation reaction of enynes and enynophiles has been developed. The use of an N-heterocyclic carbene-based palladium precursor allowed us to achieve turnover numbers up to 1800. T
- Zatolochnaya, Olga V.,Galenko, Alexey V.,Gevorgyan, Vladimir
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supporting information; experimental part
p. 1149 - 1155
(2012/06/16)
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- Asymmetric counteranion-directed transition-metal catalysis: Enantioselective epoxidation of alkenes with Manganese(III) salen phosphate complexes
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(Figure Presented) Figure Presentation Paired up: A highly active and enantioselective ion-pair epoxidation catalyst, consisting of an achiral Mn |||-salen complex and a chiral phosphate counteranion, mediates the epoxidization of a wide range of alkenes with high yields and enantioselectivities (see scheme). The unique role of the counteranion is to stabilize an enantiomorphic conformation of the cationic Mn catalyst.
- Liao, Saihu,List, Benjamin
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supporting information; experimental part
p. 628 - 631
(2010/04/06)
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- Synthesis of α-hydroxyallenes by copper-catalyzed S N2′substitution of propargylic dioxolanones
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A new catalytic method for the synthesis of α-hydroxyallenes is described. Efficient SN2′ substitution of propargylic dioxolanones has been achieved with a copper(I)/P(OBu)3 catalyst: using Grignard reagents as the nucleophiles. The
- Tang, Xiaoping,Woodward, Simon,Krause, Norbert
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experimental part
p. 2836 - 2844
(2009/09/29)
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- Enantioselective epoxidation of conjugated cis-enynes by chiral dioxirane
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(Chemical Equation Presented) This paper describes a highly chemo- and enantioselective epoxidation of conjugated cis-enynes using readily available glucose-derived ketone 2 as catalyst and Oxone as oxidant to form cis-propargyl epoxides in high ee's. The
- Burke, Christopher P.,Shi, Yian
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p. 4093 - 4097
(2008/02/04)
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- Efficient synthesis of enynes by tetraphosphine-palladium-catalysed reaction of vinyl bromides with terminal alkynes
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Through the use of [PdCl(C3H5)]2/cis,cis, cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane as catalyst, a range of vinyl bromides undergoes Sonogashira cross-coupling reaction with a variety of alkynes, leading to
- Feuerstein, Marie,Chahen, Ludovic,Doucet, Henri,Santelli, Maurice
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p. 112 - 120
(2007/10/03)
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- Palladium-catalyzed coupling reactions of functionalized styryl bromides with 1-propenyltributyltin
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The palladium-catalyzed coupling reaction of 1-propenyltributyltin with functionalized styryl bromides is described. 1,3-Dienes are obtained in low to moderate yields except with β,β-dibromostyrene.The latter undergoes a novel organotin-promoted dehydrobromination-coupling sequence to give a 1,3-enyne as final product.Key words: Tin; Palladium; Styryl bromide; Coupling reaction; Bromides; Catalysis
- Zapata, Antonio J.,Ruiz, Jacqueline
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- Asymmetric dihydroxylation of enynes
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Catalytic asymmetric dihydroxylations of 1,3-enynes were studied using 9-0-(9′-phenanthryl) dihydroquinidine (PHN-DHQD) 1 and 1,4-bis-(9-0-dihydroquinidine) phthalazine (DHQD2-PHAL) 2. Terminal olefins showed moderate (38-79% ee) and trans-disu
- Jeong, Kyu-Sung,Sjoe, Peter,Sharpless, K. Barry
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p. 3833 - 3836
(2007/10/02)
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- Enantioselective Epoxidation of Conjugated Dienes and Enynes. Trans-Epoxides from cis-Olefins
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Asymmetric epoxidation of conjugated dienes and enynes catalyzed by (salen)Mn(II) coplex I takes place with high chemoselectivity to afford monoepoxides exclusively.Reactions of cis-enynes proceed with very high levels of asymmetric induction, with trans-alkynyl epoxides as the major products.
- Lee, Nam Ho,Jacobsen, Eric N.
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p. 6533 - 6536
(2007/10/02)
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- AMMONIUM SALTS IN ALKYLATION REACTIONS. XXVI. THE BEHAVIOR OF PHENYLACETYLENE UPON ALKYLATION IN HIGHLY BASIC MEDIA
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Phenylacetylene undergoes oxidative dimerization with the formation of 1,4-diphenylbutadiyne and 1,4-diphenylbutenyne upon alkylation in a two-phase solid-liquid catalytic system.Alkylation by allyl halides in an argon atmosphere gives the alkylation product, 1-phenyl-4-penten-1-yne, which isomerizes in the reaction system to 1-phenyl-3-penten-1-yne, in addition to the dimerization products.
- Paravyan, S. L.,Torosyan, G. D.,Babayan, A. T.
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p. 631 - 634
(2007/10/02)
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