- Regioselective access to CF3S-substituted dihydrofurans from homopropargylic alcohols with trifluoromethanesulfenamide
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A facile access to 4-((trifluoromethyl)thio)-2,3-dihydrofurans from unprotected homopropargylic alcohols in high regioselectivity is reported. This method is the first example of using a free hydroxy group as a nucleophile to complete a trifluoromethylthiolation/cyclization protocol with an alkyne in moderate to excellent yields. This journal is
- Chen, Dao-Qian,Gao, Pin,Zhou, Ping-Xin,Song, Xian-Rong,Qiu, Yi-Feng,Liu, Xue-Yuan,Liang, Yong-Min
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- Stereodivergent Palladium- And Rhodium-Catalyzed Intramolecular Addition of Tosylureas to Allenes: Diastereoselective Synthesis of Tetrahydropyrimidinones
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The intramolecular addition of tosylureas to allenes is highly syn-/anti-diastereoselective when employing a palladium or rhodium-based catalytic system and affords 1,3-cyclic ureas. Under palladium catalysis a range of thermodynamic anti-tetrahydropyrimi
- Breit, Bernhard,Geissler, Arne G. A.,Riesterer, Jasmin R.
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supporting information
p. 9168 - 9172
(2021/12/06)
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- One-Pot γ-Lactonization of Homopropargyl Alcohols via Intramolecular Ketene Trapping
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A one-pot γ-lactonization of homopropargyl alcohols via an alkyne deprotonation/boronation/oxidation sequence has been developed. Oxidation of the generated alkynyl boronate affords the corresponding ketene intermediate, which is trapped by the adjacent hydroxy group to furnish the γ-lactone. We have optimized the conditions as well as examined the substrate scope and synthetic applications of this efficient one-pot lactonization.
- Yamane, Daichi,Tanaka, Haruna,Hirata, Akihiro,Tamura, Yumiko,Takahashi, Daichi,Takahashi, Yusuke,Nagamitsu, Tohru,Ohtawa, Masaki
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supporting information
p. 2831 - 2835
(2021/05/05)
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- Photoredox propargylation of aldehydes catalytic in titanium
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A practical and effective photoredox propargylation of aldehydes promoted by 10 mol % of [Cp2TiCl2] is presented. No stoichiometric metals or scavengers are used for the process. A catalytic amount of the cheap and simply prepared or
- Calogero, Francesco,Gualandi, Andrea,Di Matteo, Marco,Potenti, Simone,Fermi, Andrea,Bergamini, Giacomo,Cozzi, Pier Giorgio
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p. 7002 - 7009
(2021/05/29)
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- Silylcyclopropanes by Selective [1,4]-Wittig Rearrangement of 4-Silyl-5,6-dihydropyrans
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4-Silyl-5,6-dihydropyrans undergo remarkably selective [1,4]-Wittig rearrangements to give silylcyclopropanes in good yields. The selectivity is independent of the silyl group, but it is influenced by the electronic character of the migrating center. Elec
- Mori-Quiroz, Luis M.,Maloba, Emmanuel W.,Maleczka, Robert E.
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supporting information
p. 5724 - 5728
(2021/07/31)
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- Synthesis of vinylic sulfones in aqueous media
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A green method for the sulfination of allenic carbonyl compounds to access a wide variety of vinylic sulfones is developed. This reaction works in aqueous media under very mild conditions. This reaction is atom economic. A wide variety of vinylic sulfones could be obtained in moderate to excellent yields with wide functional group tolerance. The efficiency of this method is demonstrated in some reactions where the desired products can be isolated by filtration.
- Goh, Jeffrey,Maraswami, Manikantha,Loh, Teck-Peng
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supporting information
p. 1060 - 1065
(2021/02/16)
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- Formal metal-free γ-arylation of 1,3-dicarbonyl compounds: Via an isomerisation/1,4-addition/[3,3]-sigmatropic rearrangement sequence
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A metal-free redox arylation of alkynes with sulfoxides has been developed to provide unconventional access to diverse γ-arylated 1,3-dicarbonyl compounds in an atom-economical manner. Mechanistic studies suggest that a conjugated allenone intermediate was generated in situ, which solves the problem of reactivity and regioselectivity of unsymmetrical dialkyl-substituted internal alkynes and enables the functionalisation of a broad range of substrates bearing electron-withdrawing functional groups. The resulting arylated 1,3-dicarbonyl compounds are versatile and useful building blocks for further functionalisation. This journal is
- Guan, Xi-Dong,Lu, Shi-Chao,Wen, Fu-Qiang
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supporting information
p. 8964 - 8968
(2021/11/27)
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- Scalable Regioselective and Stereoselective Synthesis of Functionalized (E)-4-Iodobut-3-en-1-ols: Gram-Scale Total Synthesis of Fungal Decanolides and Derivatives
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A reliable protocol to synthesize both racemic and chiral (E)-4-iodobut-3-en-1-ols from aldehydes or epoxides, respectively, containing various aromatic and aliphatic substitutions has been established. The utility of these compounds was then demonstrated
- Sherwood, Alexander M.,Williamson, Samuel E.,Johnson, Stephanie N.,Yilmaz, Anil,Day, Victor W.,Prisinzano, Thomas E.
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p. 980 - 992
(2018/01/27)
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- Gold-catalyzed regioselective synthesis of 2- and 3-alkynyl furans
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Chemical Matching: C2- or C3-alkynylated furans were selectively synthesized by using gold catalysis. Direct C-H alkynylation of furans was achieved with C2 selectivity, and a domino cyclization/alkynylation process starting from allenes gave C3-alkynylat
- Li, Yifan,Brand, Jonathan P.,Waser, Jerome
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supporting information
p. 6743 - 6747
(2013/07/26)
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- Efficient synthesis of γ-lactones via gold-catalyzed tandem cycloisomerization/oxidation
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A novel Au-catalyzed tandem cycloisomerization/oxidation of homopropargyl alcohols was developed. Various γ-lactones can be accessed readily by utilizing this strategy. Notably, the mechanism of this reaction is distinctively different from the related Ru-catalyzed reactions where the ruthenium vinylidene intermediate was proposed.
- Shu, Chao,Liu, Meng-Qi,Sun, Yu-Zhe,Ye, Long-Wu
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supporting information
p. 4958 - 4961,4
(2012/12/12)
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- Efficient synthesis of γ-lactones via gold-catalyzed tandem cycloisomerization/oxidation
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A novel Au-catalyzed tandem cycloisomerization/oxidation of homopropargyl alcohols was developed. Various γ-lactones can be accessed readily by utilizing this strategy. Notably, the mechanism of this reaction is distinctively different from the related Ru-catalyzed reactions where the ruthenium vinylidene intermediate was proposed.
- Shu, Chao,Liu, Meng-Qi,Sun, Yu-Zhe,Ye, Long-Wu
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supporting information
p. 4958 - 4961
(2013/01/15)
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- Zinc catalyzed and mediated propargylations with propargyl boronates
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Chemical Equation Presented The utility of allenyl and propargyl boronates for the propargylation of aldehydes and ketones mediated by zinc is presented. The reaction is catalytic in zinc with allenyl or propargyl borolanes. The propargylation with crystalline and air-stable propargyl diethanolamine boronates was also achieved. A catalytic cycle is proposed, and preliminary mechanistic studies are discussed.
- Fandrick, Daniel R.,Fandrick, Keith R.,Reeves, Jonathan T.,Tan, Zhulin,Johnson, Courtney S.,Lee, Heewon,Song, Jinhua J.,Yee, Nathan K.,Senanayake, Chris H.
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supporting information; experimental part
p. 88 - 91
(2010/03/03)
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- Preparation of organoaluminum reagents from propargylic bromides and aluminum activated by PbCl2and their regio- And diastereoselective addition to carbonyl derivatives
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Various propargylic and allenic aluminum reagents have been easily prepared by a direct insertion of aluminum into propargylic bromides in the presence of PbCl2 (1 mol%). These organoaluminum reagents react with carbonyl compounds to afford the
- Guo, Li-Na,Gao, Hongjun,Mayer, Peter,Knochel, Paul
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supporting information; experimental part
p. 9829 - 9834
(2010/11/02)
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- Ring opening/fragmentation of dihydropyrones for the synthesis of homopropargyl alcohols
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Ring-opening/C-C bond cleavage reactions induced by nucleophilic addition of methyl Grignard to 5,6-dihydro-2-pyrone (DHP) triflates 1 furnish homopropargyl alcohols (1 → 2) stereospecifically with respect to the stereochemistry of 1. Carbonyl extrusion from DHP triflates provides a unified and operationally simple strategy for preparing chiral homopropargyl alcohols. Copyright
- Tummatorn, Jumreang,Dudley, Gregory B.
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p. 5050 - 5051
(2008/10/09)
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- Carbonyl propargylation and allenylation with 2-propynyl mesylates, tin(IV) iodide, and tetrabutylammonium iodide controlled by either a steric effect or coordination effect
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A combination of tin(IV) iodide and tetrabutylammonium iodide can be used for propargylation or allenylation of aldehydes with 2-propynyl mesylates in dichloromethane. 1-Methyl-2-propynyl mesylate or 2-butynyl mesylate results in propargylation or allenyl
- Masuyama, Yoshiro,Yamazuki, Ryouichi,Ohtsuka, Masaru,Kurusu, Yasuhiko
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p. 1750 - 1752
(2008/02/03)
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- Highly selective formation of propargyl- and allenyltrichlorosilanes and their regiospecific addition to various types of aldehydes: Preparation of both allenic and homopropargylic alcohols
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The highly selective preparation of propargyl- and allenyltrichlorosilanes via metal-catalyzed silylation of propargyl chloride has been developed. These trichlorosilyl nucleophiles were then shown to add to various types of aldehydes to afford the corres
- Schneider, Uwe,Sugiura, Masaharu,Kobayashi, Shu
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p. 496 - 502
(2007/10/03)
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- Regioselective addition reactions of propargyl bromides to carbonyl compounds with gallium catalyzed by indium
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Reactions of organogallium reagents generated from propargyl bromides having substituents at the γ-position and gallium in the presence of 5 mol % of indium with aldehydes and ketones selectively produced homoallenyl alcohols in good to excellent yields.
- Lee, Phil Ho,Kim, Hyun,Lee, Kooyeon
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p. 1219 - 1222
(2007/10/03)
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- Selective carbonyl propargylation mediated by SnCl2/NiCl 2-KI in water
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Propargylation of carbonyl compounds to produce homopropargylic alcohols plays a very important role in synthetic organic and pharmaceutical chemistry. A novel method that carbonyl compounds and propargyl halide were mediated by SnCl2/NiCl
- Wang, Jun,Miao, Xiao-Peng,Yuan, Gu
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p. 611 - 614
(2007/10/03)
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- Preparation of homoallylic homopropargylic alcohols from 2-vinyloxiranes
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(Chemical Equation Presented) β,γ-Unsaturated aldehydes generated in situ by treatment of 2-vinyloxiranes with a catalytic amount of Sc(OTf)3 or BF·OEt2 are effectively trapped by B-allenyl-9-BBN to afford homoallylic homopropargylic alcohols in high yield. An enantioselective version has been demonstrated, and a convenient synthesis of 9-allenyl-9-BBN is described.
- Maddess, Matthew L.,Lautens, Mark
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p. 3557 - 3560
(2007/10/03)
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- Carbonyl allenylations and propargylations by 3-chloro-1-propyne or 2-propynyl mesylates with tin(IV) chloride and tetrabutylammonium iodide
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By the use of tin(IV) chloride and tetrabutylammonium iodide in dichloromethane, 3-chloro-1-propyne or 2-propynyl mesylate can be applied to allenylation and propargylation of aldehydes (carbonyl allenylation and propargylation) to produce a mixture of 1-
- Masuyama, Yoshiro,Watabe, Akiko,Kurusu, Yasuhiko
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p. 1713 - 1715
(2007/10/03)
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- A highly atom efficient, solvent promoted addition of tetraallylic, tetraallenic, and tetrapropargylic stannanes to carbonyl compounds
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Tetraallylic, tetraallenic, and tetrapropargylic stannanes (0.25 equiv) react with aldehydes in methanol to provide unsaturated alcohols in good to excellent yields (56-99%). These reactions proceed exclusively with allylic rearrangement for tetra(2-butenyl)tin 2b and tetra(1,2-butadienyl)-tin 16c and predominantly with allylic rearrangement for tetrapropadienyltin 16a and tetra(2-butynyl)tin 6e. Allylation reactions also proceeded smoothly with reactive ketones such as ethyl pyruvate (9a) and cyclohexanone (9b). The corresponding TFA-catalyzed reactions of dimethyl acetals 4d and 4e are regiospecific with allylic rearrangement.
- McCluskey,Muderawan,Muntari,Young
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p. 7811 - 7817
(2007/10/03)
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- Carbonyl propargylation by 1-substituted prop-2-ynyl mesylates and carbonyl allenylation by 3-substituted prop-2-ynyl mesylates with tin(II) iodide and tetrabutylammonium iodide
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1-Substituted prop-2-ynyl mesylates cause propargylation of aldehydes with tin(II) iodide, tetrabutylammonium iodide and sodium iodide in 1,3-dimethylimidazolidin-2-one to produce 2-substituted but-3-yn-1-ols, while 3-substituted prop-2-ynyl mesylates cau
- Masuyama,Watabe,Ito,Kurusu
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p. 2009 - 2010
(2007/10/03)
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- Synthesis of substituted α-methylene-γ-butyrolactones from chloroformates via palladium catalysed cyclisation-anion capture
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Cyclisation of chloroformates onto proximate alkyne functionality in the presence of a Pd(0) catalyst followed by anion capture affords α-methylene-γ-butyrolactone derivatives in moderate to good yields.
- Grigg,Savic
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p. 2381 - 2382
(2007/10/03)
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- Gallium-mediated highly regioselective reaction of allyl-type bromide and propargyl-type bromide with aldehyde
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In the presence of potassium iodide and lithium chloride, the one-pot reaction of gallium powder, allyl-type bromide and aldehyde shows very high selectivity favoring α-adducts. Under the same condition, the reaction of propargylic bromide with aldehyde e
- Han, Ying,Chi, Zhengfa,Huang, Yao-Zeng
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p. 1287 - 1296
(2007/10/03)
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- Carbonyl propargylation or allenylation by 3-haloprop-1-yne with tin(n) halides and tetrabutylammonium halides
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3-Bromoprop-1-yne causes carbonyl propargylation with tin(n) chloride and tetrabutylammonium bromide in water to produce 1-substituted but-3-yn-1-ols, while 3-chloroprop-1-yne causes carbonyl allenylation with tin(II) iodide and tetrabutylammonium iodide in 1,3-dimethylimidazolidin-2-one to produce 1-substituted buta-2,3-dien-1-ols.
- Masuyama, Yoshiro,Ito, Akihiro,Fukuzawa, Mamiko,Terada, Kohji,Kurusu, Yasuhiko
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p. 2025 - 2026
(2007/10/03)
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- Solvent assisted addition of tetraallylic, tetraallenic and tetrapropargylic stannanes to aldehydes and acetals
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Tetraallylic, tetraallenic and tetrapropargylic stannanes (0.25 eq) react with aldehydes in methanol to provide unsaturated alcohols. These reactions proceed exclusively with allylic rearrangement for tetra(2-butenyl)tin 2b and tetra(1,2-butadienyl)tin 5e and predominantly with allylic rearrangement for tetrapropadienyltin Sc and tetra(2-butynyl)tin 6e. The corresponding TFA catalysed reactions of dimethyl acetals with Sc and 6e are highly regioselective with allylic rearrangement.
- McCluskey, Adam,Muderawari, I. Wayan,Muntari,Young, David J.
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p. 909 - 911
(2007/10/03)
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- An Effective and Selective Conjugate Propargylation Reaction of Stannylallenes to α,β-Unsaturated Carbonyl Compounds and α-Nitro Olefins
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Stannylallenes (1) reacted with α,β-unsaturated carbonyl compounds and α-nitro olefins in the presence of TiCl4 to give the corresponding conjugate propargylation products.Thus, the reaction of 1 with cyclic and acyclic α,β-unsaturated carbonyl compounds (2) gave β-propargylic ketones (3) in high yields.With α-nitro olefins (4), two types of products, β-propargylic nitroalkanes (5) and α-propargylic ketones (6), were obtained selectively depending on the presence or absence of the α-substituent of 4.Transformation of the products (6) to cyclopentenone derivatives (10 and 12) are also described.
- Haruta, Jun-ichi,Nishi, Koichi,Matsuda, Satoshi,Akai, Shuji,Tamura, Yasumitsu,Kita, Yasuyuki
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p. 4853 - 4859
(2007/10/02)
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- Chiral Allenylboronic Esters as a Practical Reagent for Enantioselective Carbon-Carbon Bond Formation. Facile Synthesis of (-)-Ipsenol
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A stereospecific synthetic route to (-)-ipsenol is described.The synthesis illustrates a new asymmetric synthetic reaction using chiral allenyl boronic esters.The scope of the synthesis as a general route to either (R)- or (S)-3-alkynol is further illustrated by several cases.
- Ikeda, Nobuo,Arai, Isao,Yamamoto, Hisashi
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p. 483 - 486
(2007/10/02)
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