5208-37-7Relevant academic research and scientific papers
One-Pot C-H Arylation/Lactamization Cascade Reaction of Free Benzylamines
Chand-Thakuri, Pratibha,Landge, Vinod G.,Kapoor, Mohit,Young, Michael C.
supporting information, p. 6626 - 6644 (2020/07/14)
An efficient method has been developed for the synthesis of seven-membered biaryl lactams involving Pd-catalyzed, native amine-directed, ortho-arylation of benzylamines followed by in situ lactamization. This cascade sequence is enabled by the use of 2-iodobenzoates, which facilitates C-H arylation from the free amine under conditions that typically require an improved directing group approach. This reaction is characterized by a broad substrate scope with good functional group tolerance. The need for an ester versus carboxylic acid-functionalized coupling partner is also explored, as is the potential for synthesizing eight-membered biaryl lactams. Various applications are also investigated, including access to the aza-brassinolide core.
Carbon Dioxide-Mediated C(sp2)-H Arylation of Primary and Secondary Benzylamines
Kapoor, Mohit,Chand-Thakuri, Pratibha,Young, Michael C.
supporting information, p. 7980 - 7989 (2019/05/22)
C-C bond formation by transition metal-catalyzed C-H activation has become an important strategy to fabricate new bonds in a rapid fashion. Despite the pharmacological importance of ortho-arylbenzylamines, however, effective ortho-C-C bond formation of free primary and secondary benzylamines using PdII remains an outstanding challenge. Presented herein is a new strategy for constructing ortho-arylated primary and secondary benzylamines mediated by carbon dioxide (CO2). The use of CO2 with Pd is critical to allowing this transformation to proceed under relatively mild conditions, and mechanistic studies indicate that it (CO2) is directly involved in the rate-determining step. Furthermore, the milder temperatures furnish free amine products that can be directly used or elaborated without the need for deprotection. In cases where diarylation is possible, an interesting chelate effect is shown to facilitate selective monoarylation.
Synthesis of 4H-1,3-Benzoxazines via Metal- and Oxidizing Reagent-Free Aromatic C-H Oxygenation
Xu, Fan,Qian, Xiang-Yang,Li, Yan-Jie,Xu, Hai-Chao
supporting information, p. 6332 - 6335 (2017/12/08)
An unprecedented electrochemical aromatic C-H oxygenation reaction for the synthesis of 4H-1,3-benzoxazines from easily available N-benzylamides is reported. These oxidative cyclization reactions proceed in a transition metal- and oxidizing reagent-free fashion and produce H2 as only theoretical byproduct. Adapting the C-H oxygenation reaction in an electrochemical microreactor has been demonstrated.
Selective reaction of benzyl alcohols with HI gas: Iodination, reduction, and indane ring formations
Matsumoto, Shoji,Naito, Masafumi,Oseki, Takehisa,Akazome, Motohiro,Otani, Yasuhiko
, p. 7254 - 7259 (2017/11/24)
Reactions of benzyl alcohols with HI in solvent-free conditions were examined. Three types of reactions (iodination, reduction, and ring formation) occurred depending on the degree of crowding around the benzyl position and the benzylic stabilization of substrates. Results also showed that the ring formation to give indanes proceeded efficiently when HI was used, and that compounds with electron-rich aromatic rings gave indane derivatives in good yields.
Access to "friedel-Crafts-Restricted" tert -alkyl aromatics by activation/methylation of tertiary benzylic alcohols
Hartsel, Joshua A.,Craft, Derek T.,Chen, Qiao-Hong,Ma, Ming,Carlier, Paul R.
experimental part, p. 3127 - 3133 (2012/05/20)
Herein we describe a two-step protocol to prepare m-tert-alkylbenzenes. The appropriate tertiary benzylic alcohols are activated with SOCl2 or concentrated HCl and then treated with trimethylaluminum, affording the desired products in 68-97% yields (22 examples). This reaction sequence is successful in the presence of a variety of functional groups, including acid-sensitive and Lewis-basic groups. In addition to t-Bu groups, 1,1-dimethylpropyl and 1-ethyl-1-methylpropyl groups can also be installed using this method.
Improved preparative route toward 3-arylcyclopropenes
Sherrill, William M.,Kim, Ryan,Rubin, Michael
, p. 8610 - 8617 (2008/12/21)
A convenient preparative protocol for the synthesis of various 3-arylcyclopropenes in a multigram scale is disclosed. Optimization of the reaction conditions and isolation procedures allowed for significant improvement of the chemical yields of these strained products. The described protocol was used for efficient preparation of a series of 3-methyl-3-arylcyclopropenes possessing different substituents in the aromatic ring. The effect of substitution in the aryl group on the stability of 3-arylcyclopropenes, as well as the corresponding precursors, is discussed.
Catalytic Oxidation of (+)-3-Carene with Oxygen
Tolstikov, G. A.,Galin, F. Z.,Ignatyuk, V. K.,Kashina, Yu. A.,Galkin, E. G.
, p. 1044 - 1046 (2007/10/03)
Liquid-phase oxidation of (+)-3-carene in the presence of catalysts with active additives (pyridine, amines, and amines) has been studied.
INTRODUCTION OF OXYGENATED FUNCTIONAL GROUPS INTO 3-CARENE AND 2-PINENE BY CULTURED CELLS
Hirata, Toshifumi,Ikeda, Yoshihiro,Izumi, Shunsuke,Shimoda, Kei,Hamada, Hiroki,Kawamura, Toshinari
, p. 401 - 404 (2007/10/02)
The biotransformation of the monoterpene hydrocarbons 3-carene and 2-pinene by cell suspension cultures of Nicotiana tabacum and Catharanthus roseus was investigated.The cultures have the ability to regio- and enantioselectively introduce the oxygenated functional groups into the C=C double bond and the allylic positions of the substrates. - Key words: Nicotiana tabacum; Solanaceae; Catharanthus roseus; Apocyanaceae; cultured cells; biotransformation; epoxidation; hydroxylation; carene; pinene.
ELECTROPHILIC ADDITION OF LEAD TETRAACETATE TO 2-CARENE IN AN ACIDIDIC MEDIUM
Arbuzov, B. A.,Isaeva, Z. G.,Belyaeva, M. G.,Ratner, V. V.,Kataeva, O. N.,et al.
, p. 117 - 119 (2007/10/02)
Oxidation of 2-carene by lead tetraacetate in acetic acid afforded p-menth-1(10),2-dien-7-ol, 2-acetyl-6,6-dimethylbicyclohexane, p-menth-2-ene-1α,7-diol, p-menth-1-ene-3β,7-diol, and 2-(m-tolyl)propanol-2.Keywords: oxidation, lead tetraacetate, 2-carene, benzene, acetic acid, medium polarity.
PRODUCTS OF THE CATALYTIC LIQUID-PHASE OXIDATION OF 3-CARENE
Vyglazov, O. G.,Manukov, E. N.,Fedorishcheva, M. N.,Ariko, N. G.,Chuiko, V. A.,Bazhina, G. N.
, p. 283 - 287 (2007/10/02)
The liquid-phase oxidation of 3-carene in the presence of various catalytic systems has been studied.The possibility has been shown of the directed preparation of 3-carene oxide, of ketones with a carane skeleton and a 7-membered ring, or of aromatic tertiary alcohols.
