共查询到20条相似文献,搜索用时 453 毫秒
1.
2.
Miura K Wang D Matsumoto Y Fujisawa N Hosomi A 《The Journal of organic chemistry》2003,68(22):8730-8732
The Et3B-initiated reaction of gamma-unsubstituted propargyl alcohols with dibutylchlorostannane (Bu2SnClH) at low temperature gave (Z)-vinylstannanes with high regio- and stereoselectivity. The corresponding alkyl propargyl ethers also underwent regio- and stereoselective homolytic hydrostannylation with Bu2SnClH; however, the regioselectivity was not so high as that with the propargyl alcohols. 相似文献
3.
It is known that Rh‐catalyzed reaction of propargylic alcohols with aryl metallic reagents undergoes SN2’‐type reaction affording allenes via a sequential arylmetalation and β‐OH elimination process. Here we report a Rh/Ag‐cocatalyzed reaction of propargylic alcohols with organoboronic acids affording stereo‐defined (E)‐3‐arylallylic alcohols via arylmetalation and protodemetalation with a high regio‐ and stereoselectivity under very mild conditions. The reaction exhibits a good substrate scope and the compatibility with synthetically useful functional groups with no racemization for optically active propargylic alcohols. Such a reaction may also be extended to homopropargylic alcohols with a remarkable regioselectivity and exclusive E‐stereoselectivity. 相似文献
4.
[Rh(CO)(2)Cl](2) is an effective catalyst for the ring opening of vinyl epoxides with alcohols and aromatic amines under neutral conditions at room temperature. The reaction occurs with excellent diastereo- and regioselectivity (>20:1) giving the trans-1,2-amino alcohols or alkoxy alcohols for a wide range of substrates. The regio- and stereochemistry of these reactions is complementary to that typically obtained with palladium-catalyzed ring openings of vinyl epoxides. 相似文献
5.
Shintaro Hatanaka Yasushi Obora Dr. Yasutaka Ishii Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(6):1883-1888
A novel iridium‐catalyzed intermolecular coupling reaction of primary alcohols or aldehydes with 2‐alkynes was successfully achieved with high regioselectivity to give hydroacylation products such as α,β‐unsaturated ketones in good yields. The mechanistic investigation of the reaction strongly indicated that the coupling proceeds through the initial formation of homoallylic alcohols followed by dehydrogenation to β,γ‐unsatutated ketones and then isomerisation, which leads to the hydroacylation products. 相似文献
6.
Alkynes (internal and terminal) and aldehydes (aromatic and aliphatic) are reductively coupled in a single catalytic reaction to yield di- and trisubstituted allylic alcohols with high stereoselectivity and regioselectivity. In most cases, a 1:1 ratio of alkyne to aldehyde is sufficient for efficient coupling. The yield and regioselectivity are strongly dependent on the phosphine ligand, but the allylic alcohols formed are invariably the products of cis addition to the alkyne. 相似文献
7.
H-Z-Y5.6 (Y-type zeolite) shows the highest activity for the ring-opening reaction of 1,2-epoxybutane, and H-Z-HM15 (mordenite type of zeolite) shows the highest regioselectivity for the formation of 2-methoxybutanol by comparing the reaction rates. The regioselectivity obtained by the zeolite using various alcohols is higher or similar than that in acidic conditions using H2SO4 catalyst. 相似文献
8.
The reaction of 3-O-substituted propynyl aluminum reagents with a TIPS-protected 2,3-epoxy alcohol and several diastereomeric 2-methyl-3,4-epoxy alcohols offers a convenient synthetic approach for the subsequent preparation and epoxidation of allylic alcohols. The yields are low to moderate and the regioselectivity (internal vs external attack) is similar to that of the standard diethylpropynyl aluminum reagent. The TMS-acetylide alane reagent gives improved yields and good regioselectivity, and is the reagent of choice for the cleavage of the hindered epoxides. This attractive methodology is applied to the elaboration of two advanced polypropionate precursor fragments. 相似文献
9.
Yu. V. Shubina D. A. Tikhomirov A. V. Eremeev 《Chemistry of Heterocyclic Compounds》1982,18(5):494-498
2-Ethynyl-substituted aziridines were obtained by the reaction of acetylenic -amino and -azido alcohols with triphenylphosphine and carbon tetrachloride in the presence of triethylamine. The cycloaddition of carbenes and diazomethane to an acetylenic imine was investigated. 2-Ethynylaziridines were obtained in the case of carbonylalkoxycarbenes. The regioselectivity of the cycloaddition of carbenes to an acetylenic imine is demonstrated.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 656–661, May, 1982. 相似文献
10.
The nucleophilic ring opening of propargyl epoxides by amines based on a silver catalyst is presented. The reaction takes place under mild conditions and features a high regioselectivity to provide an effective method for the synthesis of 2-amino homopropargyl alcohols in moderate to high yields. 相似文献
11.
Xiao-Chun Lin Yu-Mei Wang Xu Chen Pei-Ye You Kai-Ming Mo Prof. Dr. Guo-Hong Ning Prof. Dr. Dan Li 《Angewandte Chemie (International ed. in English)》2023,62(35):e202306497
Owing to the wide and growing demand for primary alcohols, the development of efficient catalysts with high regioselectivity remains a worthwhile pursuit. However, according to Markovnikov's rule, it is a challenge to obtain primary alcohols with high yields and regioselectivity from terminal alkenes or alkynes. Herein, we report the synthesis of a photosensitizing two-dimensional (2D) metal–organic framework (MOF) from cyclic trinuclear copper(I) units (Cu-CTUs) and a boron dipyrro-methene (Bodipy) ligand. The MOF features broadband light absorption, excellent photoinduced charge separation efficiency, and photochemical properties. By integrating the copper-catalyzed hydroboration and photocatalyzed aerobic oxidation, it can catalyze terminal alkenes and alkynes to produce primary alcohols via a one-pot tandem reaction with excellent regioselectivity, good overall yields in two-step reactions (up to 85 %), broad substrate compatibility (32 examples) and good reusability under mild conditions. 相似文献
12.
Wei Huang Jiahui Bai Prof. Dr. Yinlong Guo Prof. Dr. Qinglei Chong Prof. Dr. Fanke Meng 《Angewandte Chemie (International ed. in English)》2023,62(19):e202219257
Catalytic enantioselective coupling of 1,1-disubstituted allenes and aldehydes through regiodivergent oxidative cyclization followed by stereoselective protonation or reductive elimination promoted by chiral phosphine-Co complexes is presented. Such processes represent unprecedented and unique reaction pathways for Co catalysis that enable catalytic enantioselective generation of metallacycles with divergent regioselectivity accurately controlled by chiral ligands, affording a wide range of allylic alcohols and homoallylic alcohols that are otherwise difficult to access without the need of pre-formation of stoichiometric amounts of alkenyl- and allyl-metal reagents in up to 92 % yield, >98 : 2 regioselectivity, >98 : 2 dr and >99.5 : 0.5 er. 相似文献
13.
[reaction: see text] A reagent combination of beta-SnO and catalytic [Rh(COD)Cl](2) in THF-H(2)O promotes the reaction of propargyl bromides and aldehydes and directs the regioselectivity toward the formation of either allenic alcohols or homopropargylic alcohols. This highly regioselective either/or transformation proceeds via a transmetalation from rhodium to tin, in which metallotropic rearrangement between a propargylmetal and allenylmetal is arrested. 相似文献
14.
Nucleophilic Difluoromethylation of Epoxides with PhSO(NTBS)CF2H by a Preorganization Strategy
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Xiao Shen Qinghe Liu Tao Luo Prof. Dr. Jinbo Hu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(22):6795-6800
Unlike the facile synthesis of β‐monofluoromethyl alcohols by nucleophilic monofluoromethylation of epoxides, the synthesis of β‐difluoromethyl alcohols by nucleophilic difluoromethylation of epoxides still remains a challenge. Herein, studies on tackling this problem with PhSO(NTBS)CF2H ( 2 ; TBS=tert‐butyldimethylsilyl) are reported. The preorganization of 2 and epoxides with BF3 ? Et2O was found to be crucial for the reaction. The reaction shows excellent regioselectivity and has a broad substrate scope. The facile transformation of the ring‐opened products to β‐difluoromethyl, γ‐difluoromethyl, and β‐difluoromethylenyl alcohols demonstrates the synthetic utility of the reaction. 相似文献
15.
Sampak Samanta 《Tetrahedron letters》2006,47(20):3383-3386
The direct aldol reaction of 1,2-diketones and ketones mediated by proline derivatives yields the corresponding 2-hydroxy 1,4-diketones in high regioselectivity, diastereoselectivity and good enantioselectivity. This reaction provides an easy access to optically active tertiary alcohols, which are flanked by two carbonyl groups for further elaborations. 相似文献
16.
Under the conditions of ruthenium-catalyzed transfer hydrogenation, isoprene couples to benzylic and aliphatic alcohols 1a-g to deliver beta,gamma-unsaturated ketones 3a-g in good to excellent isolated yields. Under identical conditions, aldehydes 2a-g couple to isoprene to provide an identical set of beta,gamma-unsaturated ketones 3a-g in good to excellent isolated yields. As demonstrated by the coupling of butadiene, myrcene, and 1,2-dimethylbutadiene to representative alcohols 1b, 1c, and 1e, diverse acyclic dienes participate in transfer hydrogenative coupling to form beta,gamma-unsaturated ketones. In all cases, complete branch regioselectivity is observed, and, with the exception of adduct 3j, isomerization to the conjugated enone is not detected. Thus, formal intermolecular diene hydroacylation is achieved from the alcohol or aldehyde oxidation level. In earlier studies employing a related ruthenium catalyst, acyclic dienes were coupled to carbonyl partners from the alcohol or aldehyde oxidation level to furnish branched homoallylic alcohols. Thus, under transfer hydrogenative coupling conditions, all oxidation levels of substrate (alcohol or aldehyde) and product (homoallyl alcohol or beta,gamma-unsaturated ketone) are accessible. 相似文献
17.
J Zhang X Su J Fu X Qin M Zhao M Shi 《Chemical communications (Cambridge, England)》2012,48(73):9192-9194
We have found a Tf(2)O-mediated intramolecular cyclization reaction and have revealed an intriguing stereoselectivity and a regioselectivity during the preparation of intermediate alcohols, which allow for the tailor-made synthesis of various backbone-substituted imidazolinium salts, and structurally specific syn-4,5-disubstituted imidazolinium salts. 相似文献
18.
Jianlin Yang Ming Zhang Chao Dong Li-Biao Han 《Phosphorus, sulfur, and silicon and the related elements》2013,188(10):691-696
AbstractA less expensive and more environmentally friendly Zn(OTf)2-catalyzed dehydrative coupling reaction of propargyl alcohols with diarylphosphine oxides is reported. The reaction takes place under mild and solvent free conditions, and features a high regioselectivity to provide an effective method for the synthesis of some diarylphosphinyl allenes in moderate to high yields. 相似文献
19.
Visible light-induced hydroxyalkylation of 2H-benzothiazoles with alcohols via selectfluor oxidation
《中国化学快报》2020,31(12):3245-3249
A visible-light induced metal-free approach was described for the hydroxyalkylation of 2H-benzothiazoles with alcohols by using selectfluor as the oxidant. A variety of 2H-benzothiazoles and alcohols could be tolerated, providing a mild and simple method for the synthesis of C2-hydroxyalkylated 2H-benzothiazoles in moderate to good yields. Besides, ethers were also compatible in this reaction, leading to corresponding C2 ether-substituted 2H-benzothiazoles with high regioselectivity. 相似文献
20.
Epoxides react smoothly with tetraallyltin in the presence of 2 mol% of Bi(OTf)3 under mild reaction conditions to afford the corresponding homoallylic alcohols in excellent yields with high regioselectivity while aryl aziridines produce exclusively allyl amines in good yields under similar conditions. 相似文献