131428-11-0Relevant articles and documents
Novel methodology for the synthesis of n-alkoxyamines
Braslau, Rebecca,Tsimelzon, Anna,Gewandter, Jennifer
, p. 2233 - 2235 (2004)
We report a new methodology for the synthesis of the N-alkoxyamines, which can be used as initiators in "living" free radical polymerization. Silyl radical abstraction from alkyl halides allows the synthesis of N-alkoxyamines inaccessible by other methods
Metal free decarboxylative aminoxylation of carboxylic acids using a biphasic solvent system
Schulz, G?ran,Kirschning, Andreas
supporting information, p. 273 - 278 (2021/01/14)
The smooth oxidative radical decarboxylation of carboxylic acids with TEMPO and other derivatives as radical scavengers is reported. The key to success was the use of a two-phase solvent system to avoid otherwise predominant side reactions such as the oxidation of TEMPO by persulfate and enabled the selective formation of synthetically useful alkoxyamines. The method does not require transition metals and was successfully used in a new synthetic approach for the antidepressant indatraline.
Compound containing carbon-silicon bond and application thereof
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Paragraph 0411-0413, (2020/09/08)
The invention discloses a compound containing a carbon-silicon bond and application of the compound in construction of the carbon-carbon bond. The invention provides an application of a compound containing the carbon-silicon bond as shown in a formula I or a formula I' in a chemical reaction for constructing the carbon-carbon bond, wherein one carbon in the carbon-carbon bond is from carbon connected with silicon in the compound containing the carbon-silicon bond. According to the preparation method, the compound containing the carbon-silicon bond is used for providing a carbon free radical, and the carbon free radical can directly react with carbon provided in another molecule under a mild condition to construct the carbon-carbon bond; the preparation method is wider in substrate application range, is suitable for functional group activated C and carbon free radical substrates, and is also suitable for unactivated C-H bond substrates.
Harnessing Alkylpyridinium Salts as Electrophiles in Deaminative Alkyl-Alkyl Cross-Couplings
Plunkett, Shane,Basch, Corey H.,Santana, Samantha O.,Watson, Mary P.
supporting information, p. 2257 - 2262 (2019/03/04)
A Negishi cross-coupling of alkylpyridinium salts and alkylzinc halides has been developed. This is the first example of alkyl-alkyl bond formation via cross-coupling of an alkyl amine derivative with an unactivated alkyl group, and allows both primary and secondary alkylpyridinium salts to react with primary alkylzinc halides with high functional group tolerance. When combined with formation of the pyridinium salts from primary amines, this method enables the noncanonical transformation of NH2 groups into a wide range of alkyl substituents with broad functional group tolerance.
Deaminative Reductive Cross-Electrophile Couplings of Alkylpyridinium Salts and Aryl Bromides
Liao, Jennie,Basch, Corey H.,Hoerrner, Megan E.,Talley, Michael R.,Boscoe, Brian P.,Tucker, Joseph W.,Garnsey, Michelle R.,Watson, Mary P.
, p. 2941 - 2946 (2019/04/30)
A nickel-catalyzed reductive cross-coupling of alkylpyridinium salts and aryl bromides has been developed using Mn as the reductant. Both primary and secondary alkylpyridinium salts can be used, and high functional group and heterocycle tolerance is observed, including for protic groups. Mechanistic studies indicate the formation of an alkyl radical, and controlling its fate was key to the success of this reaction.
Engaging Alkenes and Alkynes in Deaminative Alkyl-Alkyl and Alkyl-Vinyl Cross-Couplings of Alkylpyridinium Salts
Baker, Kristen M.,Lucas Baca, Diana,Plunkett, Shane,Daneker, Mitchell E.,Watson, Mary P.
, p. 9738 - 9741 (2019/12/02)
An alkyl-alkyl cross-coupling of Katritzky alkylpyridinium salts and organoboranes, formed in situ via hydroboration of alkenes, has been developed. This method utilizes the abundance of both alkyl amine precursors and alkenes to form C(sp3)-C(sp3) bonds. This strategy is also effective with alkynes, enabling a C(sp3)-C(sp2) cross-coupling. Under these mild conditions, a broad range of functional groups, including protic groups, is tolerated. As seen with previous alkylpyridinium cross-couplings, mechanistic studies support an alkyl radical intermediate.
Copper-Catalyzed Decarboxylative Difluoromethylation
Zeng, Xiaojun,Yan, Wenhao,Zacate, Samson B.,Chao, Tzu-Hsuan,Sun, Xiaodong,Cao, Zhi,Bradford, Kate G. E.,Paeth, Matthew,Tyndall, Sam B.,Yang, Kundi,Kuo, Tung-Chun,Cheng, Mu-Jeng,Liu, Wei
, p. 11398 - 11403 (2019/08/20)
We report herein a highly efficient Cu-catalyzed protocol for the conversion of aliphatic carboxylic acids to the corresponding difluoromethylated analogues. This robust, operationally simple and scalable protocol tolerates a variety of functional groups and can convert a diverse array of acid-containing complex molecules to the alkyl-CF2H products. Mechanistic studies support the involvement of alkyl radicals.
Potassium Alkylpentafluorosilicates, Primary Alkyl Radical Precursors in the C-1 Alkylation of Tetrahydroisoquinolines
Wang, Teng,Wang, Dong-Hui
, p. 3981 - 3985 (2019/06/14)
In this study, we demonstrate that potassium alkylpentafluorosilicates (RSiF5K2) are efficient primary alkyl radical precursors for selective C(sp3)-C(sp3) bond-forming reactions. RSiF5K2 reagents are white, free-flowing solids and are moisture and air stable. This class of reagents enables the direct C-1 alkylation of tetrahydroisoquinolines under mild conditions via single-electron transfer. The broad substrate scope of both alkylpentafluorosilicates and tetrahydroisoquinolines is tolerated in this transformation. Both radical scavenger and EPR capture experiments show that the primary radical is generated by the oxidation of RSiF5K2. A mechanism involving alkyl radical addition to an iminium salt followed by reduction by an amine is proposed.
Facial strategy for radical species through Ag(I)-mediated oxidation of the alkyl trifluoroborates
Ding, Siyi,Tian, Shaopeng,Zhao, Yuzhen,Ma, Qiang,Zhu, Min,Ren, Huaping,Li, Kexuan,Miao, Zongcheng
supporting information, p. 936 - 945 (2018/03/21)
A rapid and highly efficient method for the radical formation using potassium alkylfluoroborates as radical precursor is devised and developed which conducts under relatively mild condition using silver(I) oxide as the oxidant. The observed silver mirror
Harnessing Alkyl Amines as Electrophiles for Nickel-Catalyzed Cross Couplings via C-N Bond Activation
Basch, Corey H.,Liao, Jennie,Xu, Jianyu,Piane, Jacob J.,Watson, Mary P.
, p. 5313 - 5316 (2017/04/27)
We developed a strategy to harness alkyl amines as alkylating agents via C-N bond activation. This Suzuki-Miyaura cross coupling of alkylpyridinium salts, readily formed from primary amines, is the first example of a metal-catalyzed cross coupling via C-N bond activation of an amine with an unactivated alkyl group. This reaction enjoys broad scope and functional group tolerance. Primary and secondary alkyl groups can be installed. Preliminary studies suggest a NiI/NiIII catalytic cycle.
