62403-86-5Relevant articles and documents
The intramolecular reaction of acetophenoneN-tosylhydrazone and vinyl: Br?nsted acid-promoted cationic cyclization toward polysubstituted indenes
Wang, Zhixin,Li, Yang,Chen, Fan,Qian, Peng-Cheng,Cheng, Jiang
, p. 1810 - 1813 (2021/02/27)
In the presence of TsNHNH2, a Br?nsted acid-promoted intramolecular cyclization ofo-(1-arylvinyl) acetophenone derivatives was developed, leading to polysubstituted indenes with complexity and diversity in moderate to excellent yields. In sharp contrast with either the radical or carbene involved cyclization of aldehydicN-tosylhydrazone with vinyl, a cationic cyclization pathway was involved, whereN-tosylhydrazone served as an electrophile and alkylation reagent during this transformation.
Divergent Access to Benzocycles through Copper-Catalyzed Borylative Cyclizations
Yoon, Wan Seok,Han, Jung Tae,Yun, Jaesook
supporting information, p. 4953 - 4959 (2021/09/14)
A copper-catalyzed chemodivergent approach to five- and six-membered benzocycles from dienyl arenes tethered with a ketone has been developed. Through proper choice of coordinating ligands and catalytic conditions, copper-catalyzed borylative cyclization of a single dienyl arene can be diverted to two different pathways, leading to indanols and dihydronaphthalenols with high stereoselectivity. The chiral bidentate bisphosphine ligand (S,S)-Ph-BPE was optimal for asymmetric copper-allyl addition to a tethered ketone via a boat-like transition state, whereas NHC ligands led to boro-allyl addition producing indanols with high diastereoselectivity. (Figure presented.).
Asymmetric Synthesis and Application of Chiral Spirosilabiindanes
Chang, Xin,Chen, Hong-Chao,Li, Chuan-Ying,Ma, Pei-Long,Wang, Peng
supporting information, p. 8937 - 8940 (2020/04/30)
Reported here is the development of a class of chiral spirosilabiindane scaffolds by Rh-catalyzed asymmetric double hydrosilation, for the first time. Enantiopure SPSiOL (spirosilabiindane diol), a new type of chiral building block for the preparation of various chiral ligands and catalysts, was readily prepared on greater than 10 gram scale using this protocol. The potential of this new spirosilabiindane scaffold in asymmetric catalysis was preliminarily demonstrated by development of the corresponding monodentate phosphoramidite ligands (SPSiPhos), which were used in both a Rh-catalyzed hydrogenation and a Pd-catalyzed intramolecular carboamination.
Synthesis of Carbamates from Alkyl Bromides and Secondary Amines Using Silver Carbonate
Acharya, Vanitha,Mal, Sanjib,Kilaru, Jagadeesh P.,Montgomery, Mark G.,Deshpande, Sudhindra H.,Sonawane, Ravindra P.,Manjunath, Bhanu N.,Pal, Sitaram
supporting information, p. 378 - 387 (2020/01/22)
Synthesis of alkyl carbamates from alkyl bromides and secondary amines using silver carbonate as a carbonate source under mild condition is described. Various secondary amines and bromo derivatives were converted into alkyl carbamate derivatives in 33 to 62 % yield.
Fe-Catalyzed Cycloisomerization of Aryl Allenyl Ketones: Access to 3-Arylidene-indan-1-ones
Teske, Johannes,Plietker, Bernd
supporting information, p. 2257 - 2260 (2018/04/27)
A cycloisomerization of aryl allenyl ketones to 3-arylidene-indan-1-ones using a cationic Fe-complex as a catalyst is reported. The catalyst opens a synthetically interesting reaction pathway to this surprisingly underrepresented class of indanones that are not accessible using alternative catalytic systems.
One-Pot Asymmetric Synthesis of Alkylidene 1-Alkylindan-1-ols Using Br?nsted Acid and Palladium Catalysis
Faggyas, Réka J.,Calder, Ewen D. D.,Wilson, Claire,Sutherland, Andrew
, p. 11585 - 11593 (2017/11/10)
A one-pot catalytic enantioselective allylboration/Mizoroki-Heck reaction of 2-bromoaryl ketones has been developed for the asymmetric synthesis of 3-methyleneindanes bearing a tertiary alcohol center. Br?nsted acid-catalyzed allylboration with a chiral BINOL derivative was followed by a palladium-catalyzed Mizoroki-Heck cyclization, resulting in selective formation of the exo-alkene. This novel protocol provides a concise and scalable approach to 1-alkyl-3-methyleneindan-1-ols in high enantiomeric ratios (up to 96:4 er). The potential of these compounds as chiral building blocks was demonstrated with efficient transformation to optically active diol and amino alcohol scaffolds.
Stereoselective Ketone Rearrangements with Hypervalent Iodine Reagents
Malmedy, Florence,Wirth, Thomas
supporting information, p. 16072 - 16077 (2016/10/30)
The first stereoselective version of an iodine(III)-mediated rearrangement of arylketones in the presence of orthoesters is described. The reaction products, α-arylated esters, are very useful intermediates in the synthesis of bioactive compounds such as ibuprofen. With chiral lactic acid-based iodine(III) reagents product selectivities of up to 73 % ee have been achieved.
Borylation of Olefin C-H Bond via Aryl to Vinyl Palladium 1,4-Migration
Hu, Tian-Jiao,Zhang, Ge,Chen, Ya-Heng,Feng, Chen-Guo,Lin, Guo-Qiang
supporting information, p. 2897 - 2900 (2016/03/19)
The aryl to vinyl palladium 1,4-migration was realized for the first time. The generated alkenyl palladium species was trapped by diboron reagents under Miyaura borylation conditions, providing a new method to synthesize β,β-disubstituted vinylboronates. The excellent regioselectivity and broad substrate scope were observed for this novel transformation.
Enantioselective Bromo-oxycyclization of Silanol
Xia, Zilei,Hu, Jiadong,Shen, Zhigao,Wan, Xiaolong,Yao, Qizheng,Lai, Yisheng,Gao, Jin-Ming,Xie, Weiqing
supporting information, p. 80 - 83 (2016/01/15)
Relying on the nucleophilicity of silanol for building up silicon-incorporated scaffold with an enantiopure tetrasubstituted carbon center remains elusive. In this report, asymmetric bromo-oxycyclization of olefinic silanol by using chiral anionic phase-transfer catalyst is described. This protocol provided a facile entry to a wide arrangement of enantiopure benzoxasilole in moderate to excellent enantioselectivities depending on the unique reactivity of bromine/N-benzyl-DABCO complex.
Synthesis of 1-indanols and 1-indanamines by intramolecular palladium(0)-catalyzed C(sp3)-H arylation: Impact of conformational effects
Janody, Simon,Jazzar, Rodolphe,Comte, Arnaud,Holstein, Philipp M.,Baudoin, Olivier,Vors, Jean-Pierre,Ford, Mark J.
supporting information, p. 11084 - 11090,7 (2014/10/15)
A range of valuable 1-indanols and 1-indanamines containing a tertiary C1 atom were synthesized by intramolecular palladium(0)-catalyzed C(sp 3)-H arylation, despite unfavorable steric interactions. The efficiency of the reaction was found to correlate with the degree of substitution at C2, as expected from the Thorpe-Ingold effect. Additionally, the nature of the heteroatomic substituent at C1 had a marked influence on the diastereoselectivity at C1 and C2; indeed, 1-indanols and 1-indanamines were obtained with the opposite relative configuration. Analysis of the X-ray and DFT-optimized structures of the corresponding reactive intermediates provided useful insights into the subtle conformational effects induced by these substituents.
