58927-86-9Relevant articles and documents
Ni0-catalyzed regio- and stereoselective coupling reaction of Me3B, isoprene, and aldehydes
Kimura,Shibata,Koudahashi,Tamaru
, p. 6789 - 6793 (2000)
In the presence of Ni(acac)2 (0.1 equiv.), the three components of trimethylborane, isoprene, find aromatic and aliphatic aldehydes' combine to produce 1-substituted 3-methyl-3-hexenols (3) in good yield and with high regio- and stereoselectivity (E:Z > 13:1). (C) 2000 Elsevier Science Ltd.
Ni-Catalyzed 1,2-Diarylation of Alkenyl Ketones: A Comparative Study of Carbonyl-Directed Reaction Systems
Apolinar, Omar,Derosa, Joseph,Engle, Keary M.,Karunananda, Malkanthi K.,Kleinmans, Roman,Li, Zi-Qi,Tran, Van T.,Wisniewski, Steven R.
supporting information, p. 5311 - 5316 (2021/07/26)
A nickel-catalyzed 1,2-diarylation of alkenyl ketones with aryl iodides and arylboronic esters is reported. Ketones with a variety of substituents serve as effective directing groups, offering high levels of regiocontrol. A representative product is diversified into a wide range of useful products that are not readily accessible via existing 1,2-diarylation reactions. Preliminary mechanistic studies shed light on the binding mode of the substrate, and Hammett analysis reveals the effect of electronic factors on initial rates.
Selective Isomerization of Terminal Alkenes to (Z)-2-Alkenes Catalyzed by an Air-Stable Molybdenum(0) Complex
Becica, Joseph,Glaze, Owen D.,Wozniak, Derek I.,Dobereiner, Graham E.
, p. 482 - 490 (2018/02/17)
Positional and stereochemical selectivity in the isomerization of terminal alkenes to internal alkenes is observed using the cis-Mo(CO)4(PPh3)2 precatalyst. A p-toluenesulfonic acid (TsOH) cocatalyst is essential for catalyst activity. Various functionalized terminal alkenes have been converted to the corresponding 2-alkenes, generally favoring the Z isomer with selectivity as high as 8:1 Z:E at high conversion. Interrogation of the catalyst initiation mechanism by 31P NMR reveals that cis-Mo(CO)4(PPh3)2 reacts with TsOH at elevated temperatures to yield a phosphine-ligated Mo hydride (MoH) species. Catalysis may proceed via 2,1-insertion of a terminal alkene into a MoH group and stereoselective β-hydride elimination to yield the (Z)-2-alkene.
Nickel-catalyzed addition of dimethylzinc to aldehydes across alkynes and 1,3-butadiene: An efficient four-component connection reaction
Kimura, Masanari,Ezoe, Akihiro,Mori, Masahiko,Tamaru, Yoshinao
, p. 201 - 209 (2007/10/03)
In the presence of 10 mol % of Ni(acac)2, four components comprising Me2Zn, alkynes, 1,3-butadiene, and carbonyl compounds combine in this order in 1:1:1:1 ratio to furnish (3E,6Z)-octadien-1-ols 1 in good yields. Similarly, the coupling reaction of Me2Zn, 1,ω-dienynes 5, and carbonyls furnishes 1-alkylidene-2-(4′-hydroxy- (1′E)-alkenyl)cyclopentanes and -cyclohexanes 6 and their oxygen and nitrogen heterocycle derivatives in good yield and an excellent level of 1,5-diastereoselectivity with respect to the cycloalkane methine carbon and the OH-bearing carbon of the C2 side chain. The reaction is completed in most cases within 1 h at room temperature under nitrogen, tolerates an ester, a hydroxy, an allyl and propargyl ethers, an allylamino, and a pyridyl functionalities, and accommodates a variety of aromatic and aliphatic alkynes and carbonyls (aldehydes and ketones).
Nickel(0)-catalyzed three-component connection reaction of dimethylzinc, 1,3-dienes, and carbonyl compounds
Kimura, Masanari,Matsuo, Shintaro,Shibata, Kazufumi,Tamaru, Yoshinao
, p. 3386 - 3388 (2007/10/03)
Linear 1:1:1 coupling of dimethylzinc, 1,3-dienes, and carbonyl compounds in this order is facilitated by catalytic amounts of [Ni(acac)2] to give (E)-3-hexen-1-ols in good yields under mild conditions [Eq. (a)]. Increasing steric hindrance at the carbonyl group favors formation of the 1:2:1 adduct, and this is the sole product when the carbonyl compound is acetone, acac = acetylacetonate.
Reaction of 1,3-dihalopropene with trialkylmanganate
Kakiya, Hirotada,Inoue, Rie,Shinokubo, Hiroshi,Oshima, Koichiro
, p. 73 - 74 (2007/10/03)
A three-component coupling reaction was performed. Treatment of 1,3-dibromopropene or 1,3-dichloropropene with tributylmanganate (n-Bu3MnLi) provided a butylated allylmanganese compound which could be trapped by an electrophile such as benzalde
Benzotriazole-mediated [2,3]-wittig rearrangement. General and stereocontrolled syntheses of homoallyl alcohols and β,γ-unsaturated ketones
Katritzky, Alan R.,Wu, Hong,Xie, Linghong
, p. 4035 - 4039 (2007/10/03)
Readily accessible allyl 1-(benzotriazol-1-yl)alkyl ethers (13 and 19), upon treatment with 2.5 equiv of nucleophilic lithium reagents, give secondary and tertiary homoallyl alcohols (16 and 21), respectively, exclusively in the E configuration in excellent yields. This is achieved by deprotonation followed by [2,3]-Wittig rearrangement, departure of the benzotriazolyl group, and then nucleophilic addition to the resulting carbonyl compound. Following a similar protocol, primary E-homoallyl alcohols 18 are prepared in good yield by the reaction of ethers 13 with LDA in the presence of NaBH4. Our approach complements the stereochemical Z-selective syntheses of primary homoallyl alcohols of Still and of Bruckner. Wittig rearrangement of the anions of 19 generated with LDA analogously furnishes E-β,γ-unsaturated ketones 20 in excellent yields.
α-Regioselective and Stereospecific Addition of Allylic Tins to Aldehydes via Photoinduced Electron Transfer
Takuwa, Akio,Shiigi, Junji,Nishigaichi, Yutaka
, p. 3457 - 3460 (2007/10/02)
(E)- and (Z)-Allylic tributyltins add to aromatic aldehydes to afford regioreversed α-adduct predominantly with almost complete retention of the stereochemistry of the allylic groups under photochemical conditions.The photoinduced single electron transfer mechanism is proposed.
One-Pot Synthesis of Substituted Homoallylic Alcohols (3-Alkenols) and 1-Deuterio-3-alkenols; II. Extension to Ketone Enolates
Barluenga, Jose,Alvarez, Flora,Concellon, Jose M.,Bernad, Pablo,Yus, Miguel
, p. 318 - 320 (2007/10/02)
The reaction of different lithium ketone enolates with α-chloro carbonyl compounds followed by in situ reduction with lithium aluminium hydride or deuteride and final lithiation with lithium powder leads to the corresponding homoallylic or 1-deuterio homoallylic alcohols in a regioselective manner.
Stereoselective Synthesis of Alcohols, XXII. E/Z-Selectivity on Addition of α-Substituted Allylboronates to Aldehydes
Hoffmann, Reinhard W.,Landmann, Bernd
, p. 1039 - 1053 (2007/10/02)
α-Heterosubstituted allylboronates 7 are prepared.Addition of 7 to aldehydes results in E/Z-isomeric homoallyl alcohols 13 and 14.The reasons for the predominant formation of the Z-isomer 14 are discussed.The Z-bromo olefins 16 and 20 obtained in this way serve as starting point for chain extension or formation of δ-lactones 21.
