- Dynamic Kinetic Cross-Electrophile Arylation of Benzyl Alcohols by Nickel Catalysis
-
Catalytic transformation of alcohols via metal-catalyzed cross-coupling reactions is very important, but it typically relies on a multistep procedure. We here report a dynamic kinetic cross-coupling approach for the direct functionalization of alcohols. The feasibility of this strategy is demonstrated by a nickel-catalyzed cross-electrophile arylation reaction of benzyl alcohols with (hetero)aryl electrophiles. The reaction proceeds with a broad substrate scope of both coupling partners. The electron-rich, electron-poor, and ortho-/meta-/para-substituted (hetero)aryl electrophiles (e.g., Ar-OTf, Ar-I, Ar-Br, and inert Ar-Cl) all coupled well. Most of the functionalities, including aldehyde, ketone, amide, ester, nitrile, sulfone, furan, thiophene, benzothiophene, pyridine, quinolone, Ar-SiMe3, Ar-Bpin, and Ar-SnBu3, were tolerated. The dynamic nature of this method enables the direct arylation of benzylic alcohol in the presence of various nucleophilic groups, including nonactivated primary/secondary/tertiary alcohols, phenols, and free indoles. It thus offers a robust alternative to existing methods for the precise construction of diarylmethanes. The synthetic utility of the method was demonstrated by a concise synthesis of biologically active molecules and by its application to peptide modification and conjugation. Preliminary mechanistic studies revealed that the reaction of in situ formed benzyl oxalates with nickel, possibly via a radical process, is an initial step in the reaction with aryl electrophiles.
- Guo, Peng,Wang, Ke,Jin, Wen-Jie,Xie, Hao,Qi, Liangliang,Liu, Xue-Yuan,Shu, Xing-Zhong
-
supporting information
p. 513 - 523
(2021/01/12)
-
- Benzyne 1,2,4-Trisubstitution and Dearomative 1,2,4-Trifunctionalization
-
Both 1,2,4-trisubstitution and dearomative 1,2,4-trifunctionalization of benzyne have been accomplished from sulfoxides bearing a penta-2,4-dien-1-yl moiety. These cascade transformations proceed through a benzyne insertion into the S═O bond and an uncommon regiospecific anionic [4,5]-sigmatropic rearrangement, furnishing a C-O, C-S, and C-C bond on the C1-, C2-, and C4-position of a benzene ring, respectively. This study showcases new cascade benzyne reaction modes involving both distal C-H bond functionalization and dearomatization.
- Chen, Zhonghong,Dai, Liang,Lan, Yu,Li, Lianggui,Li, Yang,Shan, Chunhui,Shi, Jiarong,Tan, Min
-
supporting information
p. 10530 - 10536
(2021/07/28)
-
- Benzyne-Mediated Esterification Reaction
-
A benzyne-mediated esterification of carboxylic acids and alcohols under mild conditions has been realized, which is made possible via a selective nucleophilic addition of carboxylic acid to benzyne in the presence of alcohol. After a subsequent transesterification with alcohol, the corresponding esters can be produced efficiently. This benzyne-mediated protocol can be used on the modification of Ibuprofen, cholesterol, estradiol, and synthesis of nandrolone phenylpropionate. In addition, benzyne can also be used to promote lactonization and amidation reaction.
- Li, Yang,Shi, Jiarong,Zhao, Jinlong
-
supporting information
p. 7274 - 7278
(2021/10/01)
-
- Stereoretentive Ring-Opening Metathesis Polymerization to Access All- cis Poly(p-phenylenevinylene)s with Living Characteristics
-
Poly(p-phenylenevinylene)s (PPVs), a staple of the conductive polymer family, consist of alternating alkene and phenyl groups in conjugation. The physical properties of this organic material are intimately linked to the cis/trans configuration of the alkene groups. While many synthetic methods afford PPVs with all-trans stereochemistry, very few deliver the all-cis congeners. We report herein a synthesis of all-cis PPVs with living characteristics via stereoretentive ring-opening metathesis polymerization (ROMP). Exquisite catalyst control allows for the preparation of homopolymers or diblock copolymers with perfect stereoselectivity, narrow dispersities, and predictable average molar masses. All-cis PPVs can then serve as light-responsive polymers through clean photoisomerization of the stilbenoid units.
- Hsu, Ting-Wei,Kim, Cheoljae,Michaudel, Quentin
-
supporting information
p. 11983 - 11987
(2020/08/06)
-
- Access to Highly Functionalized Indanes from Arynes and α,γ-Diketo Esters
-
An unprecedented method for the synthesis of highly functionalized indanes from arynes and α,γ-diketo esters is described. Importantly, mild and nearly pH-neutral conditions ensure excellent functional group tolerance. Theoretical studies indicated that t
- Hu, Wanyao,Zhang, Cong,Huang, Jie,Guo, Yingying,Fu, Zhenqian,Huang, Wei
-
supporting information
p. 941 - 945
(2019/05/16)
-
- Trifluoromethyl aryl sulfonates (TFMS): An applicable trifluoromethoxylation reagent
-
Fluorine is probably another favorite hetero-atom for incorporation into small molecules after nitrogen. Among many fluorine-containing groups, trifluoromethyl aryl ethers (ArOCF3) have unique properties in drug design and are difficult to be synthesized, and many different methods were developed to prepare them. A novel one-pot synthesis of o-iodine-aryl trifluoromethyl ethers (ArOCF3I) was described by the reaction of trifluoromethoxylation and iodination with trifluoromethyl aryl sulfonates (TFMS) in this manuscript. The reaction conditions were optimized by screening different solvents, crown ethers, substrates and the ratios and the yields of products were in moderate to high yields (up to 86%).
- Lei, Meng,Miao, Hang,Wang, Xueyuan,Zhang, Wen,Zhu, Chengjian,Lu, Xiaqiang,Shen, Jian,Qin, Yanru,Zhang, Haoyang,Sha, Sijia,Zhu, Yongqiang
-
supporting information
p. 1389 - 1392
(2019/04/30)
-
- Construction of Phenanthrenes and Chrysenes from β-Bromovinylarenes via Aryne Diels-Alder Reaction/Aromatization
-
A highly efficient transition-metal-free general method for the synthesis of polycyclic aromatic hydrocarbons like phenanthrenes and chrysenes (and tetraphene) from β-bromovinylarenes and arynes has been developed. The reactions proceed via an aryne Diels-Alder (ADA) reaction, followed by a facile aromatization. This is the first report on direct construction of chrysenes (and tetraphene) using the ADA approach. Unlike the literature method which is limited to only 9/10-substituted derivatives, this method gives access to a wide variety of functionalized phenanthrenes.
- Singh, Vikram,Verma, Ram Subhawan,Khatana, Anil K.,Tiwari, Bhoopendra
-
supporting information
p. 14161 - 14167
(2019/10/28)
-
- Transition-Metal-Free Benzannulation of Tricarbonyl Derivatives with Arynes: Access to 1,3-Dinaphthol Precursors for the Synthesis of Rhodamine Dye Analogues
-
Herein, we report a transition-metal-free annulation reaction of benzynes and 1,3-oxopentanedioate for the synthesis of highly functionalized naphthalene derivatives for the first time. Additionally, the representative naphthalene derivatives have been successfully transformed into the new series of rhodamine dye analogues.
- Ghotekar, Ganesh S.,Shaikh, Aslam C.,Muthukrishnan
-
p. 2269 - 2276
(2019/05/16)
-
- A facile route to 1: H- A nd 2 H-indazoles from readily accessible acyl hydrazides by exploiting a novel aryne-based molecular rearrangement
-
Herein we report the transformation of readily synthesised acyl hydrazides into 2-hydrazobenzophenones via a novel molecular rearrangement pathway using aryne chemistry. The developed reaction protocol is performed under relatively mild conditions and is
- Shamsabadi, André,Chudasama, Vijay
-
supporting information
p. 11180 - 11183
(2018/10/15)
-
- Tandem nucleophilic addition-cycloaddition of arynes with α-iminoesters: Two concurrent pathways to imidazolidines
-
The tandem nucleophilic addition-cycloaddition reaction has been developed for the synthesis of functionalized imidazolidine derivatives. A variety of α-iminoesters and aryne precursors were well tolerated under the mild reaction conditions. This asymmetric cycloaddition afforded imidazolidine derivatives with high yields, complete regioselectivities, and excellent diastereo- and enantioselectivities. Aryne-induced ylides working as 1,3-dipoles for asymmetric cycloaddition are the notable feature of the present reaction. In the tandem reaction, the [3+2] cycloaddition of aryne-induced ylides with metallized α-iminoesters and metal-catalyzed [3+2] cycloaddition of azomethine ylide with α-iminoesters are two concurrent pathways to imidazolidines.
- Jia, Hao,Guo, Zhenyan,Liu, Honglei,Mao, Biming,Shi, Xueyan,Guo, Hongchao
-
supporting information
p. 7050 - 7053
(2018/07/05)
-
- A 2 - (trimethyl silicon-based) phenyl trifluoro methane sulfonate synthetic method (by machine translation)
-
The invention discloses a 2 - (trimethyl silicon-based) phenyl trifluoro methane sulfonate synthetic method, characterized in that in the 2 - bromophenol in the carboxylic adds by drops six silicon [...], and milling the ripening after; the reaction in th
- -
-
Paragraph 0039; 0040; 0041; 0042; 0043; 0044; 0045-0052
(2017/12/05)
-
- Synthesis of o-Aryloxy Triarylsulfonium Salts via Aryne Insertion into Diaryl Sulfoxides
-
The aryne insertion into "S-O" bond has been validated recently. This technology is elusively applied to the synthesis of thioethers. In contrast to the reported cases, the reaction described furnished o-aryloxy triarylsulfonium salts, in lieu of thioethe
- Li, Xiaojin,Sun, Yan,Huang, Xin,Zhang, Lei,Kong, Lichun,Peng, Bo
-
supporting information
p. 838 - 841
(2017/02/26)
-
- Selective: S -arylation of 2-oxazolidinethiones and selective N -arylation of 2-benzoxazolinones/2-benzimidazolinones
-
There exist three possible patterns for the reaction of cyclic 2-oxazolidinethione and 2-benzoxazolidinethione with arynes, namely (a) S-arylation, (b) N-arylation, and (c) aryne insertion into the thiocarbonyl group (CS). Our studies demonstrate that S-arylation wins out affording S-aryl dihydrooxazoles. In contrast, for related reactions of cyclic 2-benzoxazolinone and 2-benzimidazolinone with arynes, it is found that N-arylation outcompetes O-arylation and aryne insertion into the CO group to give N-aryl 2-benzoxazolinones and N-aryl 2-benzimidazolinones.
- Sun, Chu-Han,Lu, Yi,Zhang, Qing,Lu, Rong,Bao, Lin-Qing,Shen, Mei-Hua,Xu, Hua-Dong
-
p. 4058 - 4063
(2017/07/10)
-
- Alkyl substituted [2.2]paracyclophane-1,9-dienes
-
[2.2]Paracyclophane-1,9-dienes substituted with n-octyl chains have been synthesised from the corresponding dithia[3.3]paracyclophanes using a benzyne induced Stevens rearrangement. The use of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate and tetra-n-butylammonium fluoride as the in situ benzyne source gave significantly improved yields over traditional sources of benzyne and enabled the preparation of n-octyl substituted [2.2]paracyclophane-1,9-dienes on a multi-gram scale.
- Lidster, Benjamin J.,Kumar, Dharam R.,Spring, Andrew M.,Yu, Chin-Yang,Helliwell, Madeleine,Raftery, James,Turner, Michael L.
-
supporting information
p. 6079 - 6087
(2016/07/06)
-
- Continuous-flow synthesis of trimethylsilylphenyl perfluorosulfonate benzyne precursors
-
2-(Trimethylsilyl)phenyl perfluorosulfonated aryne precursors may now be accessed using flow chemistry, enabling the fast preparation of pure compounds with no requirement for low temperature lithiation or column chromatography. The process has been adapted to novel nonaflate precursors, utilizing the cheaper and more user-friendly nonaflyl fluoride reagent. The resultant nonaflates are shown to successfully participate in a range of aryne reaction classes.
- Michel, Boris,Greaney, Michael F.
-
supporting information
p. 2684 - 2687
(2014/06/09)
-
- Acetic acid promoted metal-free aerobic carbon-carbon bond forming reactions at α-position of tertiary amines
-
The oxidative functionalization of the benzylic C-H bonds in tetrahydroisoquinolines and tetrahydro-β-carboline derivatives was investigated. C-C bond forming reactions proceeded with a range of nucleophiles (nitroalkane, enol silyl ether, indole, allylstannane, and tetrabutylammonium cyanide) under metal-free conditions and an oxygen atmosphere. Acetic acid caused a significant acceleration effect.
- Ueda, Hirofumi,Yoshida, Kei,Tokuyama, Hidetoshi
-
supporting information
p. 4194 - 4197
(2014/09/30)
-
- Insertion of arynes into arylphosphoryl amide bonds: One-step simultaneous construction of C-N and C-P bonds
-
The insertion of arynes into arylphosphoryl amide bonds to synchronously construct C-P and C-N bonds is described. Arynes generated in situ from o-triflate arylsilanes under fluoride-promoted conditions insert into relatively inert P-N bonds, producing o-
- Shen, Chaoren,Yang, Guoqiang,Zhang, Wanbin
-
supporting information
p. 5722 - 5725
(2013/12/04)
-
- Regioselective synthesis of 2-(2-hydroxyaryl)pyridines from the reactions of benzynes with pyridine N-oxides
-
By modifying the conditions from those in Larock's reported synthesis of 3-(2-hydroxyaryl)pyridines from benzynes, and pyridine N-oxides, we altered the regioselectivity of the reaction toward an efficient synthesis of 2-substituted pyridines. The presenc
- Shaibu, Balagopal S.,Kawade, Rahul Kisan,Liu, Rai-Shung
-
p. 6834 - 6839
(2012/11/07)
-
- Synthesis of aryl stannanes from silyl triflates via aryne intermediates
-
Aryl stannanes are easily accessible from o-silylated aryl triflates in the presence of KF and Bu3SnH. The corresponding arynes are formed in situ, and undergo clean hydrostannation to give a mixture of the regioisomeric aryl stannanes. The whole reaction sequence can also be carried out as a one-pot reaction under microwave irradiation. Georg Thieme Verlag Stuttgart New York.
- Lakshmi, B. Vasantha,Wefelscheid, Ulrike K.,Kazmaier, Uli
-
supporting information; experimental part
p. 345 - 348
(2011/04/15)
-
- Improved synthesis of the benzyne precursor 2-(trimethylsilyl)phenyl trifluoromethanesulfonate
-
An alternate procedure for the preparation of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate, a coveted benzyne precursor, is described. Modifications to existing methods result in a dramatic reduction in the overall reaction time and eliminate the us
- Atkinson, Darcy J.,Sperry, Jonathan,Brimble, Margaret A.
-
experimental part
p. 911 - 913
(2010/04/29)
-
- Efficient synthesis of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate: A versatile precursor to o-benzyne
-
(Chemical Equation Presented) An efficient procedure for the gram-scale preparation of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate, a versatile precursor to o-benzyne, is presented. The three-step sequence utilizes phenol as the starting material, requires only one chromatographic purification, and ultimately delivers the desired silyltriflate in 66% overall yield. 2009 American Chemical Society.
- Bronner, Sarah M.,Garg, Neil K.
-
experimental part
p. 8842 - 8843
(2010/02/28)
-
- An efficient procedure for the synthesis of ortho-trialkylsilylaryl triflates: Easy access to precursors of functionalized arynes
-
o-Trialkylsilylaryl triflates which are useful aryne precursors are prepared from o-bromophenols by an efficient, one-pot procedure involving O-silylation, metal-halogen exchange, O- to C-silyl migration, and entrapment of the phenoxide with triflic anhydride.
- Pena, Diego,Cobas, Agustin,Perez, Dolores,Guitian, Enrique
-
p. 1454 - 1458
(2007/10/03)
-
- FLUORIDE-INDUCED 1,2-ELIMINATION OF O-TRIMETHYLSILYLPHENYL TRIFLATE TO BENZYNE UNDER MILD CONDITIONS
-
Fluoride-induced 1,2-elimination of o-trimethylsilylphenyl triflate provided a convenient route to benzyne under mild conditions where detriflation from an intermediary aryl anion appeared to occur in preference to protonation even in the presence of alcohols.
- Himeshima, Yoshio,Sonoda, Takaaki,Kobayashi, Hiroshi
-
p. 1211 - 1214
(2007/10/02)
-