- Synthesis of chiral diferrocenyl diselenides and their application to asymmetric reactions
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Two optically active diferrocenyl diselenides, each of which possesses two chiral centers, were newly prepared from commercial 1-(dimethylamino)ethylferrocenes and applied to induce highly enantioselective selenoxide elimination producing axially chiral allenecarboxylic esters.
- Nishibayashi,Nishibayashi, Yoshiaki,Singh,Singh, Jai Deo,Uemura,Uemura, Sakae,Fukuzawa,Fukuzawa, Shin-Ichi
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- PPh3-catalyzed β-selective addition of α-fluoro β-dicarbonyl compounds to allenoates
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A highly selective phosphine-catalyzed β-addition of α-fluoro β-dicarbonyl compounds to allenoates has been developed. Both α-fluoro β-diketones and α-fluoro β-keto esters prove to be competent fluorocarbon nucleophiles, giving a series of the β-addition products bearing a fluorinated quaternary carbon center in good to excellent yields and with excellent regioselectivities. A plausible reaction pathway is presented.
- Liu, Yong-Liang,Wang, Xiao-Ping,Wei, Jie,Li, Ya
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supporting information
(2021/12/02)
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- Phosphine-Catalyzed Asymmetric Tandem Isomerization/Annulation of Allyl Amines with Allenoates: Enantioselective Annulation of a Saturated C-N Bond
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Under catalysis by chiral phosphine, an asymmetric isomerization/annulation cascade reaction of allylamines with allenoates was realized. A wide range of γ-substituted allenoates were tolerated to afford chiral pyrroline derivatives in high yields with excellent enantioselectivities. In the reaction, isomerization of readily available N-allylamines to reactive aliphatic imines through a 1,4-proton shift is a key step, which circumvents the isolation of highly unstable alkyl N-sulfonylimines.
- Zhou, Leijie,Zhang, Xue,Wang, Qijun,Liu, Min,Wang, Wei,Wu, Yongjun,Chen, Liezhong,Guo, Hongchao
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supporting information
p. 9173 - 9178
(2021/11/30)
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- NHC-Catalyzed Aldol-Like Reactions of Allenoates with Isatins: Regiospecific Syntheses of γ-Functionalized Allenoates
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An N-heterocyclic carbene (NHC) catalyzed γ-specific aldol-like reaction between allenoates and isatins has been achieved under mild conditions, giving trisubstituted allene derivatives bearing isatin moiety in moderate to good yields with high diastereoselectivity and excellent atom efficiency. The DFT computations indicated that the formation of the γ-adduct was more energetically favorable than that of the α-adduct. The result reported herein opens a new route for NHC-promoted allenoate-involved reaction.
- Li, Sha,Tang, Ziwei,Wang, Yang,Wang, Dan,Wang, Zhanlin,Yu, Chenxia,Li, Tuanjie,Wei, Donghui,Yao, Changsheng
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supporting information
p. 1306 - 1310
(2019/02/26)
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- Metal-Free Transfer Hydroiodination of C-C Multiple Bonds
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The design and a gram-scale synthesis of a bench-stable cyclohexa-1,4-diene-based surrogate of gaseous hydrogen iodide are described. By initiation with a moderately strong Br?nsted acid, hydrogen iodide is transferred from the surrogate onto C-C multiple bonds such as alkynes and allenes without the involvement of free hydrogen iodide. The surrogate fragments into toluene and ethylene, easy-to-remove volatile waste. This hydroiodination reaction avoids precarious handling of hydrogen iodide or hydroiodic acid. By this, a broad range of previously unknown or difficult-to-prepare vinyl iodides can be accessed in stereocontrolled fashion.
- Chen, Weiqiang,Walker, Johannes C. L.,Oestreich, Martin
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supporting information
p. 1135 - 1140
(2019/01/11)
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- Phosphine-catalyzed regiodivergent annulations of γ-substituted allenoates with conjugated dienes
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A phosphine catalyzed regiodivergent annulation of γ-substituted allenoates with conjugated dienes is reported, and highly functionalized cyclohexenes or cyclopentenes were obtained in high yields and regioselectivities. This transformation takes advantag
- Gan, Zhenjie,Gong, Yanchuan,Chu, Yunpeng,Li, Er-Qing,Huang, You,Duan, Zheng
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p. 10120 - 10123
(2019/08/30)
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- Nickel-catalyzed, ligand-free, diastereoselective synthesis of 3-methyleneindan-1-ols
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Nickel-catalyzed, highly diastereoselective annulations between activated allenes and 2-acetylarylboronic acid or 2-formylarylboronic acids are reported. No ligand for nickel is required, and the reactions proceed efficiently at room temperature to give a broad range of substituted 3-methyleneindan-1-ols. Preliminary results of an enantioselective variant are also described.
- Panchal, Heena,Clarke, Christopher,Bell, Charles,Karad, Somnath Narayan,Lewis, William,Lam, Hon Wai
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supporting information
p. 12389 - 12392
(2018/11/20)
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- Efficient and regioselective one-pot synthesis of S-vinyl dithiocarbamates from electron-deficient allenes, amines and CS2
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A novel and efficient one-pot procedure for the synthesis of S-vinyl dithiocarbamates from electron-deficient allenes, amines and CS2was presented. The reactions proceed at room temperature for 10–30?min without any catalyst to afford the products in high yields, excellent regioselectivity and stereoselectivity.
- Li, Ridong,Leng, Penglin,Liu, Bin,Wang, Xin,Ge, Zemei,Li, Runtao
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supporting information
p. 5707 - 5712
(2016/08/23)
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- Highly enantioselective, intermolecular hydroamination of allenyl esters catalyzed by bifunctional phosphinothioureas
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Bifunctional phosphinothiourea catalysts have been developed successfully for the highly regio- and enantioselective γ-hydroamination of allenyl and propargyl esters with N-methoxy carbamate nucleophiles to yield α,β-unsaturated γ-amino acid ester products. In the case of propargyl ester substrates, the reaction proceeds through reversible phosphinothiourea-catalyzed isomerization to the corresponding allenyl ester. The high enantioselectivity of the process is attributed to a cooperative conjugate addition of a thiourea-bound carbamate anion to a vinyl phosphonium ion resulting from covalent activation of the allenyl ester substrate.
- Fang, Yuan-Qing,Tadross, Pamela M.,Jacobsen, Eric N.
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supporting information
p. 17966 - 17968
(2015/03/03)
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- Copper-catalyzed, C-C coupling-based one-pot tandem reactions for the synthesis of benzofurans using o-iodophenols, acyl chlorides, and phosphorus ylides
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One-pot reactions involving acyl chlorides, phosphorus ylides, and o-iodophenols with copper catalysis have been established for the rapid synthesis of functionalized benzofurans. With all of these easily available and stable reactants, the construction o
- Liu, Yunyun,Wang, Hang,Wan, Jie-Ping
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p. 10599 - 10604
(2015/02/19)
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- One step synthesis of benzoxazepine derivatives via a PPh3 catalyzed aza-MBH domino reaction between salicyl N-tosylimines and allenoates
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PPh3-Catalyzed aza-MBH domino reaction of salicyl N-tosylimines with γ-CH3 substituted allenoates is reported. Readily available imines and allenoates are converted to benzoxazepine derivatives in one step. Wherein, functionalization
- Zhao, Hongxia,Meng, Xiangtai,Huang, You
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supporting information
p. 10513 - 10515
(2013/11/06)
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- Regio- and stereoselective copper-catalyzed β-borylation of allenoates by a preactivated diboron
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A mild and efficient copper-catalyzed borylation of electron deficient allenoates using an sp2-sp3 mixed hybridized diboron regioselectively installs a boron moiety on the β-position with exclusive (Z)-double bond geometry.
- Thorpe, Steven B.,Guo, Xi,Santos, Webster L.
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supporting information; scheme or table
p. 424 - 426
(2011/02/28)
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- Syntheses of spirocyclic oxindole-butenolides by using three-component cycloadditions of isocyanides, allenoates, and isatins
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Spiro workflow! Efficient syntheses of spirocyclic oxindole-butenolides from readily available isocyanides, allenoates, and isatins are disclosed (see scheme; R1=alkyl, aryl; R2=halide, nitro, methoxy; PG=protecting group). This protocol also allows the insertion of carbon monoxide into organic molecules without the aid of a transition-metal catalyst after the hydrolysis process. Copyright
- Li, Jian,Liu, Yuejin,Li, Chunju,Jia, Xueshun
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supporting information; experimental part
p. 7409 - 7413
(2011/08/05)
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- Allene carboxylates as dipolarophiles in Rh-catalyzed carbonyl ylide cycloadditions
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Face-to-face: Allene carboxylates can serve as efficient dipolarophiles for Rh-catalyzed carbonyl ylide cycloadditions (see scheme). The endo and exo products arise from cycloaddition on the same face of the allene, but opposite faces of the dipole. This facial selectivity results in the formation of two of the four possible diastereomers.
- Rout, Laxmidhar,Harned, Andrew M.
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supporting information; experimental part
p. 12926 - 12928
(2010/05/19)
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- Small-molecule inhibitors of protein geranylgeranyltransferase type I
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Small molecules that inhibit the geranylgeranylation of K-Ras4B and RhoA by protein geranylgeranyltransferase type I (GGTase-I) were identified from chemical genetic screens of heterocycles synthesized through phosphine catalysis of allenes. To further improve the efficacy of the GGTase-I inhibitors (GGTIs), 4288 related compounds bearing core dihydropyrrole/pyrrolidine and tetrahydropyridine/piperidine scaffolds were synthesized on SynPhase lanterns in a split-pool manner through phosphine-catalyzed [3 + 2] and [4 + 2] annulations of resin-bound allenoates. Testing of the 4288 analogues resulted in several GGTIs exhibiting submicromolar IC50 values. Because proteins such as Ras and Rho GTPases are implicated in oncogenesis and metastasis, these GGTIs might ultimately lead to the development of novel antitumor therapeutics. Copyright
- Castellano, Sabrina,Fiji, Hannah D. G.,Kinderman, Sape S.,Watanabe, Masaru,De Leon, Pablo,Tamanoi, Fuyuhiko,Kwon, Ohyun
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p. 5843 - 5845
(2008/03/14)
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- Reaction of 2,3-allenoates with TsNBr2 in the presence of base: A facile highly stereoselective synthesis of (1E,2E)-3-bromo-4-oxo-N′- tosyl-2-alkenoxylimidic acid ethyl esters
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(Chemical Equation Presented) A novel reaction pathway of 2,3-allenoates with an electrophile (TsNBr2) in the presence of K2CO 3 to produce (1E,2E)-3-bromo-4-oxo-N′-tosyl-2-alkenoxylimidic acid ethyl esters is reported. Th
- Shen, Ruwei,Huang, Xian
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p. 3961 - 3964
(2008/02/01)
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- Reaction of allenyl esters with sodium azide: An efficient synthesis of E-vinyl azides and polysubstituted pyrroles
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(Chemical Equation Presented) The nucleophilic addition of sodium azide to 1,2-allenyl esters can generate vinyl azides in excellent yields with excellent regio- and stereoselectivities. Moreover, pyrroles are synthesized using 1-allyllic 1,2-allenyl este
- Huang, Xian,Shen, Ruwei,Zhang, Tiexin
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p. 1534 - 1537
(2008/04/18)
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- Highly efficient [2 + 2] intramolecular cyclizations of allenynes under microwave irradiation: Construction of fused bicyclic compounds
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A palladium [2 + 2] cycloaddition of 1,6- and 1,7- allenyne carboxylates and microwave-mediated [2 + 2] cycloaddition of various 1,n-allenynes were developed and, particularly, the microwave irradiated [2 + 2] cycloaddition of allenynes can provide a simp
- Oh, Chang Ho,Gupta, Arun Kumar,Park, Dai In,Kim, Nakjoong
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p. 5670 - 5672
(2007/10/03)
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- A Short Synthesis of Allene- and Cumulenecarboxylates
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It is shown that carboxylic acids, in the presence of Bu3N and 2-chloro-1-methylpyridinium iodide in toluene or CH2Cl2, react with phosphoranes to yield the corresponding esters of allene carboxylic acids (cf.Scheme
- Kohl-Mines, Elisabeth,Hansen, Hans-Juergen
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p. 2244 - 2248
(2007/10/02)
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- Eine einfache Allencarbonsaeureester-Synthese mittels der Wittig-Reaktion
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A simple one-pot synthesis of variously substituted α-allenic esters (7-23, cf.Scheme 4) is described.Either of the phosphonium salts 1 and 2 or the phosphoranes 3-6 in methylene chloride (or acetonitrile) when treated with acid chlorides at room temperat
- Lang, Robert W.,Hansen, Hans-Juergen
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p. 438 - 455
(2007/10/02)
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