84212-92-0Relevant academic research and scientific papers
Direct preparation of allylic indium(III) reagents from allylic alcohols via a reductive transmetalation of π-allylnickel(II) with indium(I) iodide
Hirashita, Tsunehisa,Kambe, Shinya,Tsuji, Hiromitsu,Omori, Hideki,Araki, Shuki
, p. 5054 - 5059 (2004)
InI-mediated direct allylation of carbonyl compounds with allylic alcohols proceeded smoothly with catalytic amounts of Ni(acac)2 and PPh 3 to give the corresponding homoallylic alcohols in high yields. Allylindium compounds were shown to be the real allylating agents in the present system. Substituted allylic alcohols gave branched homoallylic alcohols with syn-selectivity irrespective of the geometry of the starting allylic alcohols, whereas high anti-selectivity was observed when a bulky substituent is present in the allylic alcohols. The outcome of the diastereoselectivity is discussed on the basis of the reaction mechanism, comparing with the corresponding Pd-catalyzed version. Another distinct behavior between the Ni- and Pd-catalyzed allylation was demonstrated in the reaction of hex-1,5-diene-3,4-diol derivatives: the Pd catalyst did not give any coupling product, whereas the Ni-catalyzed InI-mediated reaction with benzaldehyde afforded the 1:1 and 1:2 adduct diols selectively depending on the reaction conditions.
Catalytic Nucleophilic Allylation Driven by the Water-Gas Shift Reaction
Denmark, Scott E.,Matesich, Zachery D.,Nguyen, Son T.,Milicevic Sephton, Selena
, p. 23 - 48 (2018/02/19)
The ruthenium-catalyzed allylation of aldehydes with allylic pro-nucleophiles has been demonstrated to be an efficient means to form carbon-carbon bonds under mild conditions. The evolution of this reaction from the initial serendipitous discovery to its general synthetic scope is detailed, highlighting the roles of water, CO, and amine in the generation of a more complete catalytic cycle. The use of unsymmetrical allylic pro-nucleophiles was shown to give preferential product formation through the modulation of reaction conditions. Both (E)-cinnamyl acetate and vinyl oxirane were efficiently used to form the anti-branched products (up to >20:1 anti/syn) and E-linear products (up to >20:1 E/Z) in high selectivity with aromatic, α,β-unsaturated, and aliphatic aldehydes, respectively. Attempts to render the reaction enantioselective are highlighted and include enantioenrichment of up to 75:25 for benzaldehyde.
Chelation versus Non-Chelation Control in the Stereoselective Alkenyl sp2 C?H Bond Functionalization Reaction
Liang, Qiu-Ju,Yang, Chao,Meng, Fei-Fan,Jiang, Bing,Xu, Yun-He,Loh, Teck-Peng
supporting information, p. 5091 - 5095 (2017/04/24)
A hydroxy group chelation-assisted stereospecific oxidative cross-coupling reaction between alkenes was developed under mild reaction conditions. In the presence of palladium catalyst, the alkenes tethered with hydroxy functionality can couple efficiently with electron-deficient alkenes to form the corresponding multi-substituted olefin products. The hydroxy group on the substrate could play dual roles in reaction, acting as the directing group for alkenyl C?H bond activation and controlling the stereoselectivity of the products.
Manganese-Promoted Oxidative Cyclization of Unsaturated Oximes Using Molecular Oxygen in Air under Ambient Conditions
Yamamoto, Daisuke,Oguro, Takuto,Tashiro, Yuuki,Soga, Masayuki,Miyashita, Kazuhito,Aso, Yoshiaki,Makino, Kazuishi
supporting information, p. 5216 - 5219 (2016/11/13)
A highly efficient manganese-promoted oxidative cyclization of unsaturated oximes to afford the corresponding 4,5-dihydroisoxazoline alcohols was developed. A very low loading (generally 0.1–0.2 mol-%) of Mn(acac)3(acac = acetylacetonate) promoted the oxidative cyclization through the direct incorporation of molecular oxygen present in air (open flask) at room temperature.
Synthesis and reactivity of 1,2-dioxolanes from β,γ-epoxy ketones
Kandur, Wynne V.,Richert, Kathleen J.,Rieder, Curtis J.,Thomas, Andrew M.,Hu, Chunhua,Ziller, Joseph W.,Woerpel
supporting information, p. 2650 - 2653 (2014/06/09)
Five-membered ring peroxides were prepared in one step in 31-86% yield from readily accessible β,γ-epoxy ketones and H2O2. The reaction proceeded via a tetrahydrofuran, which was converted to the thermodynamically favored 1,2-dioxola
Catalytic, nucleophilic allylation of aldehydes with 2-substituted allylic acetates: Carbon-carbon bond formation driven by the water-gas shift reaction
Denmark, Scott E.,Matesich, Zachery D.
, p. 5970 - 5986 (2014/07/21)
The ruthenium-catalyzed allylation of aldehydes with allylic acetates has been expanded to incorporate substituents at the 2-position of the allylic components. Allylic acetates bearing a variety of substituents (CO 2-t-Bu, COMe, Ph, CH(OEt)su
Hydroxyl-directed stereoselective diboration of alkenes
Blaisdell, Thomas P.,Caya, Thomas C.,Zhang, Liang,Sanz-Marco, Amparo,Morken, James P.
supporting information, p. 9264 - 9267 (2014/07/21)
An alkoxide-catalyzed directed diboration of alkenyl alcohols is described. This reaction occurs in a stereoselective fashion and is demonstrated with cyclic and acyclic homoallylic and bishomoallylic alcohol substrates. After oxidation, the reaction generates 1,2-diols such that the process represents a method for the stereoselective directed dihydroxylation of alkenes.
Palladium-catalyzed cross-coupling of unactivated alkenes with acrylates: Application to the synthesis of the C13-C21 fragment of palmerolide A
Wen, Zhen-Kang,Xu, Yun-He,Loh, Teck-Peng
supporting information, p. 13284 - 13287,4 (2012/12/12)
Diene to meet: A palladium-catalyzed cross-coupling reaction between alkyl-substituted olefins and acrylates gives the corresponding butadienes in moderate yield and stereoselectivity. This atom-economical reaction, which forms C sp 2-C sp 2 bonds, tolerates a wide range of allylic and homoallylic alcohols, and acrylates (see scheme; TIPS =triisopropylsilyl). The methodology was applied to the synthesis of the C13-C21 fragment of palmerolide A.
Palladium-catalyzed cross-coupling of unactivated alkenes with acrylates: Application to the synthesis of the C13-C21 fragment of palmerolide A
Wen, Zhen-Kang,Xu, Yun-He,Loh, Teck-Peng
supporting information, p. 13284 - 13287 (2013/01/15)
Diene to meet: A palladium-catalyzed cross-coupling reaction between alkyl-substituted olefins and acrylates gives the corresponding butadienes in moderate yield and stereoselectivity. This atom-economical reaction, which forms C sp 2-C sp 2 bonds, tolerates a wide range of allylic and homoallylic alcohols, and acrylates (see scheme; TIPS =triisopropylsilyl). The methodology was applied to the synthesis of the C13-C21 fragment of palmerolide A.
Stereoselective synthesis of the C9-C19 fragment of lyngbyaloside B and C via ether transfer
Stefan, Eric,Taylor, Richard E.
supporting information; experimental part, p. 3490 - 3493 (2012/08/13)
A stereoselective synthesis of the C9-C19 fragment of lyngbyaloside B and C highlighted, by an extension of our ether transfer methodology, enables the formation of tertiary ethers. 2-Naphthylmethyl ethers have been shown to proceed efficiently through ether transfer with high stereoselectivity and are easily deprotected by DDQ oxidation. Variation of the workup conditions results in the stereoselective formation of syn-1,3-diol mono- or diethers.
