7111-66-2Relevant academic research and scientific papers
Dialkyl Ether Formation by Nickel-Catalyzed Cross-Coupling of Acetals and Aryl Iodides
Arendt, Kevin M.,Doyle, Abigail G.
, p. 9876 - 9880 (2015/08/19)
A new substrate class for nickel-catalyzed C(sp3) cross-coupling reactions is reported. α-Oxy radicals generated from benzylic acetals, TMSCl, and a mild reductant can participate in chemoselective cross-coupling with aryl iodides using a 2,6-bis(N-pyrazolyl)pyridine (bpp)/Ni catalyst. The mild, base-free conditions are tolerant of a variety of functional groups on both partners, thus representing an attractive C-C bond-forming approach to dialkyl ether synthesis. Characterization of a [(bpp)NiCl] complex relevant to the proposed catalytic cycle is also described.
Efficient synthesis of functionalized 1,3-dihydroisobenzofurans from salicylaldehydes: Application to the synthesis of escitalopram
Wang, Peng,Zhang, Rui,Cai, Jin,Chen, Jun-Qing,Ji, Min
, p. 549 - 552 (2014/05/06)
An efficient synthesis of substituted 1,3-dihydroisobenzofurans is developed. In this novel route, o-aroylbenzaldehydes, as key intermediates, can be obtained by lead tetraacetate oxidation of N-aroylhydrazones of salicylaldehydes. The mild and general st
C-F bond cleavage by intramolecular SN2 reaction of alkyl fluorides with O- and N-nucleophiles
Zhang, Laijun,Zhang, Wei,Liu, Jun,Hu, Jinbo
supporting information; experimental part, p. 2850 - 2853 (2009/08/08)
The nueleophilic substitution of alkyl fluorides was achieved in the intramolecular reactions with O- and N-nucleophiles. The intramolecular defluorinative cyclization reaction was influenced by the nature of nucleophiles, the size of the ring to be forme
Lanthanide(III) triflate-catalyzed thermal- and microwave-assisted synthesis of benzyl ethers from benzyl alcohols
Handlon, Anthony L.,Guo, Yu
, p. 111 - 114 (2007/10/03)
The lanthanide(III) trifluoromethanesulfonate-catalyzed condensation of benzyl alcohols with primary and secondary alcohols is described. This reaction proceeds readily with benzyl alcohols that have an alkyl or aryl substituent at the α-, ortho-, or para-position using microwave radiation or heating. The intra-molecular variant of this reaction leads to cyclic benzofurans.
Reactivity of functionalized arylcarbenes. 2-Phenylethyl side chains and hetero analogues
Kirmse, Wolfgang,Konrad, Wolfgang,Oezkir, Ismail S.
, p. 9935 - 9964 (2007/10/03)
Phenylcarbenes with -X-CH2Ph and -CH2-X-Ph (X = CH2, O, SiMe2) groups in the ortho position were generated thermally and photolytically from diazo or tosylhydrazone precursors. Stereorandom insertion reactions with β-C-H bonds were observed, pointing to a triplet abstraction-recombination mechanism. Large kinetic and stereochemical deuterium isotope effects support this notion. The ample formation of benzocyclobutenes from 2-CH2-X-Ph substrates is due to insertion of the carbenes into ArCH2-X bonds. Addition to the terminal phenyl groups competes with C-H and C-X insertion. The results of benzophenone sensitization and of trapping with methanol suggest that the intramolecular reactions of functionalized arylcarbenes proceed, at best, competitively with spin inversion.
Experiments Concerning the Reactions of Benzocyclopropene under Yb(fod)3 Catalysis
Neidlein, Richard,Kraemer, Bettina
, p. 353 - 356 (2007/10/02)
1,3-Dihydroisobenzofuran derivatives 3a-e and 5a-c are obtained by reactions of α,β-unsaturated carbonyl compounds with benzocyclopropene (1).The yields increase by addition of Yb(fod)3.Aromatic aldehydes react in the same way.Yb(fod)3 has no influence on
Carbenes and the O-H Bond: Hydroxyalkyl-Substituted Arylcarbenes
Kirmse, Wolfgang,Kund, Klaus
, p. 2325 - 2332 (2007/10/02)
carbene (4), phenylcarbene (19), and carbene (30) have been generated by photolysis of tosylhydrazone or diazo precursors in protic solvents.These carbenes give cyclic ethers (7, 18, 33) competitively with insertion into O-H bonds of the solvent.For comparison, the analogous benzyl cations (9, 17, 31) have been generated by solvolysis or dediazoniation.The cations are more sensitive to structural variation than their carbenic counterparts: 9 does not undergo intramolecular nucleophilic substitution, in contrast to 17 and 31.These observations are explicable in terms of high barriers for rotation about aryl-cation bonds, as compared with low barriers for rotation about aryl-carbene bonds.Two major effects of the solvent (ROH) and of the base (RONa) on product formation may be distinguished: (i) protonation of the carbene (or of its precursors) in the more acidic media leads to predominantly cationic processes; (ii) deprotonation of the OH group under strongly basic conditions enhances the nucleophilicity of the oxygen, and also facilitates insertion into the α-C-H bonds of 30.
Direct ortho-Metalation of Benzyl Alcohols. A Novel Method of Preparing ortho-Substituted Benzyl Alcohols
Meyer, Norbert,Seebach, Dieter
, p. 1304 - 1319 (2007/10/02)
Benzyl alcohol and other phenylcarbinols (8a - 11a), including α-tetralol (12a), are doubly deprotonated by excess n-butyllithium/TMEDA in pentane to give lithium ortho-lithioalkoxides (2, 8b - 12b).Alkylations (-> 3a - d, table 1), reactions with heteroelectrophiles (-> 3e - k, table 2) and with carbonyl compounds (-> 6, 13 - 17, tables 3 and 4), as well as subsequent reactions of the primary adducts (-> phthalanes 7, table 3) furnish a large variety of ortho-substituted benzyl alcohol derivatives.The scope and limitations of the dilithioorganyls (sections B and C), their mode of formation (section A), and attempts to doubly metalate 2-phenylethanol are discussed.
