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1.
One‐Pot Synthesis of Allylic Sulfones,Ketosulfones, and Triflyl Allylic Alcohols from Domino Reactions of Allylic Alcohols with Sulfinic Acid under Metal‐Free Conditions 下载免费PDF全文
Xue‐Qiang Chu Hua Meng Prof. Dr. Xiao‐Ping Xu Prof. Dr. Shun‐Jun Ji 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(32):11359-11368
A metal‐free tandem procedure by using a sulfonylation reaction of aryl allylic alcohols followed by an iodobenzenediacetate (PIDA)‐promoted oxidative functionalization has been established. Allylic sulfones, γ‐ketosulfones, and triflyl allylic alcohols have been constructed in a single operation. The methodology incorporates the sulfonyl (both aryl and triflyl) functionality with a simple work‐up procedure. 相似文献
2.
[reaction: see text] An efficient allylic etherification of aliphatic alcohols with allylic carbonates has been achieved by an iridium catalysis using stoichiometric zinc alkoxides or a two-component bimetallic catalytic system where the Ir(I) catalyst acts on allylic carbonates to generate electrophiles while aliphatic alcohols are separately activated by Zn(II) coordination to function as nucleophilies. This reaction occurs with complete regiospecificity and tolerates a wide range of functional groups. 相似文献
3.
Asymmetric Allylic Alkylation of β‐Ketoesters with Allylic Alcohols by a Nickel/Diphosphine Catalyst 下载免费PDF全文
Dr. Yusuke Kita Dr. Rahul D. Kavthe Hiroaki Oda Prof. Dr. Kazushi Mashima 《Angewandte Chemie (International ed. in English)》2016,55(3):1098-1101
Asymmetric allylic alkylation of β‐ketoesters with allylic alcohols catalyzed by [Ni(cod)2]/(S)‐H8‐BINAP was found to be a superior synthetic protocol for constructing quaternary chiral centers at the α‐position of β‐ketoesters. The reaction proceeded in high yield and with high enantioselectivity using various β‐ketoesters and allylic alcohols, without any additional activators. The versatility of this methodology for accessing useful and enantioenriched products was demonstrated. 相似文献
4.
Asymmetric Cascade Reaction to Allylic Sulfonamides from Allylic Alcohols by Palladium(II)/Base‐Catalyzed Rearrangement of Allylic Carbamates 下载免费PDF全文
Dipl.‐Chem. Johannes Moritz Bauer Dr. Wolfgang Frey Prof. Dr. René Peters 《Angewandte Chemie (International ed. in English)》2014,53(29):7634-7638
A regio‐ and enantioselective tandem reaction is reported capable of directly transforming readily accessible achiral allylic alcohols into chiral sulfonyl‐protected allylic amines. The reaction is catalyzed by the cooperative action of a chiral ferrocene palladacycle and a tertiary amine base and combines high step‐economy with operational simplicity (e.g. no need for inert‐gas atmosphere or catalyst activation). Mechanistic studies support a PdII‐catalyzed [3,3] rearrangement of allylic carbamates—generated in situ from the allylic alcohol and an isocyanate—as the key step, which is followed by a decarboxylation. 相似文献
5.
Haoquan Li Dr. Helfried Neumann Prof. Dr. Matthias Beller 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(29):10050-10056
A benign and efficient palladium‐catalyzed aminocarbonylation reaction of allylic alcohols is presented. The generality of this novel process is demonstrated by the synthesis of β,γ‐unsaturated amides including aliphatic, cinnamyl, and terpene derivatives. The choice of ligand is crucial for optimal carbonylation processes: Whereas in most cases the combination of PdCl2 with Xantphos ( L6 ) gave best results, sterically hindered substrates performed better in the presence of simple triphenylphosphine ( L10 ), and primary anilines gave the best results using cataCXium® PCy ( L8 ). The reactivity of the respective catalyst system is significantly enhanced by addition of small amounts of water. Mechanistic studies and control experiments revealed a tandem allylic alcohol amination/C?N bond carbonylation reaction sequence. 相似文献
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7.
Bencong Zhu Tao Shen Xiaoqiang Huang Yuchao Zhu Song Song Ning Jiao 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(32):11144-11148
Aerobic epoxidation of tertiary allylic alcohols remains a significant challenge. Reported here is an efficient and highly chemoselective copper‐catalyzed epoxidation and semipinacol rearrangement reaction of tertiary allylic alcohols with molecular oxygen. The solvent 1,4‐dioxane activates dioxygen, thereby precluding the addition of a sacrificial reductant. 相似文献
8.
Xiaoyun Wu Dr. Wei Ma Prof. Dr. Weijun Tang Prof. Dr. Dong Xue Prof. Dr. Jianliang Xiao Prof. Dr. Chao Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(60):e202201829
Allylic amines are useful building blocks in organic synthesis, so the development of green and efficient methods for the preparation of allylic amines are of great importance. An Fe-catalyzed amidation of allylic alcohols with chiral tert-butylsulfinamide has been developed. With water as the only by-product, a range of synthetically useful chiral sulfinamide olefin derivatives (30 examples) were obtained under mild reaction conditions. The reaction can be performed on a gram-scale, and the products could serve as chiral ligands for asymmetric catalysis. Mechanistic studies suggest that the reaction proceeds by an Fe-catalyzed borrowing hydrogen process, which is different from most of the reported allylic amination reactions. 相似文献
9.
Yasuaki Nakayama Ruriko Sekiya Hiroki Oishi Naoto Hama Miki Yamazaki Dr. Takaaki Sato Prof. Dr. Noritaka Chida 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(36):12052-12058
This article describes the details of two new types of Overman rearrangement from allylic vicinal diols. Starting from identical diols, both bis(imidate)s and cyclic orthoamides were selectively synthesized by simply changing the reaction conditions. Whilst exposure of the bis(imidate)s to thermal conditions initiated the double Overman rearrangement to introduce two identical nitrogen groups in a single operation (the cascade‐type Overman rearrangement), the reaction of cyclic orthoamides resulted in a single rearrangement (the orthoamide‐type Overman rearrangement). The newly generated allylic alcohols from the orthoamide‐type reaction can potentially undergo a variety of further transformations. For instance, we demonstrated an Overman/Claisen sequence in one pot. The most conspicuous feature of this method is that it offers precise control over the number of Overman rearrangements from the same allylic vicinal diols. This method also excludes the tedious protecting‐group manipulations of the homoallylic alcohols, which are necessary in conventional Overman rearrangements. All of the performed rearrangements proceeded in a completely diastereoselective fashion through a chair‐like transition state. 相似文献
10.
Ahlsten N Bartoszewicz A Martín-Matute B 《Dalton transactions (Cambridge, England : 2003)》2012,41(6):1660-1670
Allylic alcohols can be isomerised into carbonyl compounds by transition metal complexes. In the last few years, catalyst design and development have resulted in highly efficient isomerisations under mild reaction conditions, including enantioselective versions. In addition, the isomerisation of allylic alcohols has been combined with C-C bond forming reactions when electrophiles such as aldehydes or imines were present in the reaction mixture. Also, C-F bonds can be formed when electrophilic fluorinating reagents are used. Thus, allylic alcohols can be treated as latent enol(ate)s. In this article, we highlight the latest developments concerning the isomerisation of allylic alcohols into carbonyl compounds, focusing in particular on tandem isomerisation/C-C or C-heteroatom bond formation processes. Significant attention is given to the mechanistic aspects of the reactions. 相似文献
11.
Subramani Rajkumar Shunlong He Xiaoyu Yang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(30):10421-10425
A highly enantioselective kinetic resolution of tertiary 2‐alkoxycarboxamido allylic alcohols has been achieved through a chiral phosphoric acid catalyzed intramolecular transesterification reaction. Both alkyl,aryl‐ and dialkyl‐substituted tertiary allylic alcohols were resolved with excellent efficiencies, affording both the recovered tertiary alcohols and the carbamate products with high enantioselectivities (with s factors up to 164.6). A gram‐scale reaction with 1 mol % catalyst loading and the facile conversion of the enantioenriched products into useful chiral building blocks, such as chiral oxazolidinones and β‐amino alcohols, demonstrate the value of this reaction. 相似文献
12.
From a Sequential to a Concurrent Reaction in Aqueous Medium: Ruthenium‐Catalyzed Allylic Alcohol Isomerization and Asymmetric Bioreduction 下载免费PDF全文
Dr. Nicolás Ríos‐Lombardía Dr. Cristian Vidal Elisa Liardo Dr. Francisco Morís Dr. Joaquín García‐Álvarez Dr. Javier González‐Sabín 《Angewandte Chemie (International ed. in English)》2016,55(30):8691-8695
The ruthenium‐catalyzed redox isomerization of allylic alcohols was successfully coupled with the enantioselective enzymatic ketone reduction (mediated by KREDs) in a concurrent process in aqueous medium. The overall transformation, formally the asymmetric reduction of allylic alcohols, took place with excellent conversions and enantioselectivities, under mild reaction conditions, employing commercially and readily available catalytic systems, and without external coenzymes or cofactors. Optimization resulted in a multistep approach and a genuine cascade reaction where the metal catalyst and biocatalyst coexist from the beginning. 相似文献
13.
Greice Tabarelli Marcelo Godoi Rômulo F. S. Canto José R. Mora Faruk Nome 《合成通讯》2014,44(23):3441-3449
We present herein a new catalyst-free and solvent-free approach for the synthesis of allylic thioethers directly from allylic alcohols and thiols. The methodology allows the synthesis of different allylic thioethers in good to excellent yields under microwave irradiation. Theoretical calculations for the allylic carbocation helped to explain the regioselectivity observed when nonsymmetric substrates are used in the reaction. 相似文献
14.
Palladium-Catalyzed Low Pressure Carbonylation of Allylic Alcohols by Catalytic Anhydride Activation
Dr. Mathias Schelwies Dr. Rocco Paciello Dr. Ralf Pelzer Dr. Wolfgang Siegel Dr. Michael Breuer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(36):9263-9266
A direct carbonylation of allylic alcohols has been realized for the first time with high catalyst activity at low pressure of CO (10 bar). The procedure is described in detail for the carbonylation of E-nerolidol, an important step in a new BASF-route to (−)-ambrox. Key to high activities in the allylic alcohol carbonylation is the finding that catalytic amounts of carboxylic anhydride activate the substrate and are constantly regenerated with carbon monoxide under the reaction conditions. The identified reaction conditions are transferrable to other substrates as well. 相似文献
15.
Optically-active allylic alcohols have been frequently used as chiral building blocks for the preparation of optically pure compounds.1 There are at present various methods for the synthesis of optically active allylic alcohols including the kinetic resolution racemic allylic alcohols,2 reductive rearrangement of 2,3-epoxy alcohol by metal, halide and telluium-based chemistry.3 To our knowledge, One-pot Transformation of 2,3-epoxy alcohols into allylic alcohols, especially via epoxy iodides,is limited to Dorta's method3 using a Ph3P,iodine, imidazole,2,6-lutidine and water system. The original Dorta's method can be successfully applied to the formation of tertiary allylic alcohols, but give unsatisfactory results in formation of secondary allylic alcohols. 相似文献
16.
Romualdo Caputo Carla Ferreri Luigi Longobardo Domenico Mastroianni Giovanni Palumbo Silvana Pedatella 《合成通讯》2013,43(9):1223-1229
A new high yielding coupling reaction of C-2 monosubstituted 5,6-dihydro-1,4-dithiins with aldehydes is reported. In this way allylic alcohols having the cis-substituted double bond tied up by a sulfur-containing ring can be readily prepared. Subsequent stereoselective sulfur removal then affords allylic alcohols with cis-configurated double bond. 相似文献
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Dr. Naoki Ishida Yusuke Masuda Sho Uemoto Prof. Dr. Masahiro Murakami 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(19):6524-6527
A photo‐induced carboxylation reaction of allylic C?H bonds of simple alkenes with CO2 is prompted by means of a ketone and a copper complex. The unique carboxylation reaction proceeds through a sequence of an endergonic photoreaction of ketones with alkenes forming homoallyl alcohol intermediates and a thermal copper‐catalyzed allyl transfer reaction from the homoallyl alcohols to CO2 through C?C bond cleavage. 相似文献
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The treatment of α-silylated allylic alcohols with epoxidizing reagents afforded in a highly stereocontrolled fashion α-silylated aldols. The transformation is proposed to proceed either by a reaction cascade involving stereospecific epoxidation of the allylic-alcohol moiety followed by an acid-supported pinacol-type rearrangement, or by a sequence consisting of a π-face-selective electrophilic attack at the allylic silane moiety with hyperconjugative stabilization of the evolving carbocation, followed by rearrangement of the thus obtained pentacoordinated silanium ion (see Scheme 3). Depending on the reaction conditions, the π-face selectivity of the oxidation step is controlled by the stereogenic C-atom or the more remote Si-center of chirality. 相似文献