16277-67-1Relevant academic research and scientific papers
Absolute reactivity of arylallyl carbocations
Hallett-Tapley, Geniece,Cozens, Frances L.,Schepp, Norman P.
, p. 343 - 348 (2009)
A series of α-vinyl arylmethyl cations were generated and studied using nanosecond laser flash photolysis. Rate constants for the decay of the substituted α-vinyl arylmethyl cations were determined under solvolytic conditions in pure solvents and solvent
Deamination of trans-2-Methyl- And trans-2-Phenylcyclopropylamines
Wiberg, Kenneth B.,Oesterle, Carmen G.
, p. 7756 - 7762 (1999)
The deaminations of trans-2-methyl- and 2-phenylcyclopropylamine hydrochlorides in acetic acid solution have been examined. A major product in each case was an allylic chloride, and the amount of chlorides increased when the chloride ion concentration was increased. With the methyl-substituted amine, increasing the chloride ion concentration changed the major chloride product from crotyl chloride to methallyl chloride. The addition of lithium perchlorate led to a reduction in the amount of chlorides formed. These results indicate that an ion pair is involved in the reaction. The deamination of the related open chain amines gave only small amounts of chlorides. B3LYP/ 6-31G* calculations found cyclopropyldiazonium chloride to prefer to have the chloride ion over the cyclopropyl ring. The transition state was located, and when followed down to products, allyl chloride was found. Similar calculations for the methyl-substituted series led to crotyl chloride from the ion pair with one chloride ion and to methallyl chloride from the ion-triplet with two chloride ions. The deaminations of the corresponding nitrosoureas in basic methanol also were studied. The products were the expected ethers. The addition of azide ion led to azides that were largely formed by initial reaction with the diazonium ion to give a pentazene that lost nitrogen to give the azide. However, some of the azide was formed by an SN2 displacement.
Synthesis and antimicrobial properties of new derivatives of morpholine and piperidine based on 1-Chloro-3-methoxy-propylbenzene
Duruskari,Maharramov,Hasanova,Ganbarov,Eyvazova,Israyilova,Maharramov
, p. 269 - 272 (2018)
The compounds 1-(3-methoxy-1-phenyl-propyl)morpholine and 1-(3-methoxy-1-phenyl-propyl)piperidine have been synthesized using (3-methoxy-propenyl)benzene and 1-chloro-3-methoxy-propylbenzene. The structures of the synthesized compounds were analyzed by NM
Asymmetric Cu-Catalyzed 1,4-Dearomatization of pyridines and pyridazines without preactivation of the heterocycle or nucleophile
Gribble, Michael W.,Guo, Sheng,Buchwald, Stephen L.
, p. 5057 - 5060 (2018)
We show that a chiral copper hydride (CuH) complex catalyzes C-C bond-forming dearomatization of pyridines and pyridazines at room temperature. The catalytic reaction operates directly on free heterocycles and generates the nucleophiles in situ, eliminati
Palladium-catalyzed cross-coupling of organozirconium compounds with diaryliodonium salts
Huang, Xian,Sun, Ai-Ming
, p. 773 - 778 (1998)
The palladium-catalyzed cross-coupling reaction of diaryliodonium salts with organozirconium compounds was achieved for about 1-1.5 hrs at room temperature and the reaction proceeded with retention of configuration to provide a new convenient method for the synthesis of (E)-disubstituted alkenes.
Decarboxylative cross-nucleophile coupling via ligand-to-metal charge transfer photoexcitation of Cu(ii) carboxylates
Li, Qi Yukki,Gockel, Samuel N.,Lutovsky, Grace A.,DeGlopper, Kimberly S.,Baldwin, Neil J.,Bundesmann, Mark W.,Tucker, Joseph W.,Bagley, Scott W.,Yoon, Tehshik P.
, p. 94 - 99 (2022/01/11)
Reactions that enable carbon–nitrogen, carbon–oxygen and carbon–carbon bond formation lie at the heart of synthetic chemistry. However, substrate prefunctionalization is often needed to effect such transformations without forcing reaction conditions. The development of direct coupling methods for abundant feedstock chemicals is therefore highly desirable for the rapid construction of complex molecular scaffolds. Here we report a copper-mediated, net-oxidative decarboxylative coupling of carboxylic acids with diverse nucleophiles under visible-light irradiation. Preliminary mechanistic studies suggest that the relevant chromophore in this reaction is a Cu(ii) carboxylate species assembled in situ. We propose that visible-light excitation to a ligand-to-metal charge transfer (LMCT) state results in a radical decarboxylation process that initiates the oxidative cross-coupling. The reaction is applicable to a wide variety of coupling partners, including complex drug molecules, suggesting that this strategy for cross-nucleophile coupling would facilitate rapid compound library synthesis for the discovery of new pharmaceutical agents. [Figure not available: see fulltext.].
Oxoammonium-Mediated Allylsilane–Ether Coupling Reaction
Carlet, Federica,Bertarini, Greta,Broggini, Gianluigi,Pradal, Alexandre,Poli, Giovanni
supporting information, p. 2162 - 2168 (2021/04/02)
A new C(sp3)?H functionalization reaction consisting of the oxidative α-allylation of allyl- and benzyl- methyl ethers has been developed. The C?C coupling could be carried out under mild conditions thanks to the use of cheap and green oxoammonium salts. The scope of the reaction was studied over 27 examples, considering the nature of the substituents on the two coupling partners.
Unlocking Amides through Selective C–N Bond Cleavage: Allyl Bromide-Mediated Divergent Synthesis of Nitrogen-Containing Functional Groups
Govindan, Karthick,Chen, Nian-Qi,Chuang, Yu-Wei,Lin, Wei-Yu
supporting information, p. 9419 - 9424 (2021/11/30)
We report a new set of reactions based on the unlocking of amides through simple treatment with allyl bromide, creating a common platform for accessing a diverse range of nitrogen-containing functional groups such as primary amides, sulfonamides, primary amines, N-acyl compounds (esters, thioesters, amides), and N-sulfonyl esters. The method has potential industrial applicability, as demonstrated through gram-scale syntheses in batch and in a continuous flow system.
Spontaneous conversion of prenyl halides to acids: application in metal-free preparation of deuterated compounds under mild conditions
Darshana, Dhanushka,Kittakoop, Prasat,Mahidol, Chulabhorn,Ruchirawat, Somsak,Sureram, Sanya
supporting information, p. 7390 - 7402 (2021/09/07)
Here we reveal a simple generation of deuterium halide (DX) from common and inexpensive reagents readily available in a synthetic chemistry laboratory,i.e. prenyl-, allyl-, and propargyl halides, under mild conditions. We envisaged thatin situgeneration of an acid, deuterium halide, would be useful for acid-catalyzed reactions and could be employed for organocatalytic deuteration. The present work reports a metal-free method for deuterium labeling covering a broad range of substrate including phenolic compounds (i.e. flavonoids and stilbenes), indoles, pyrroles, carbonyl compounds, and steroids. This method was also applied for commonly used drugs such as loxoprofen, haloperidol, stanolone, progesterone, androstenedione, donepezil, ketorolac, adrenosterone, cortisone, pregnenolone, and dexamethasone. A gram-scale chromatography-free synthesis of some deuterated compounds is demonstrated in this work. This work provides a simple, clean and by-product-free, site-selective deuteration, and the deuterated products are obtained without chromatographic separation. When applying these initiators for other acid-catalyzed reactions, the deuterium isotope effects of DX may provide products which are different from those obtained from reactions using common acids. Although the mechanism of the spontaneous transformation of prenyl halides to acid is unclear, this overlooked chemistry may be useful for many reactions.
Nickel-Catalyzed Arylation of C(sp3)-O Bonds in Allylic Alkyl Ethers with Organoboron Compounds
Li, Xiaowei,Li, Yuxiu,Zhang, Zhong,Shi, Xiaolin,Liu, Ruihua,Wang, Zemin,Li, Xiangqian,Shi, Dayong
supporting information, p. 6612 - 6616 (2021/09/02)
A nickel-catalyzed cross-coupling of allylic alkyl ethers with organoboron compounds through the cleavage of the inert C(sp3)-O(alkyl) bonds is described. Several types of allylic alkyl ethers can be coupled with various boronic acids or their derivatives to give the corresponding products in good to excellent yields with wide functional group tolerance and excellent regioselectivity. The gram-scale reaction and late-stage modification of biologically active compounds further prove the practicality of this synthetic method.
