2506-41-4Relevant articles and documents
Visible-Light-Induced Vicinal Dichlorination of Alkenes through LMCT Excitation of CuCl2
Li, Jingjing,Lian, Pengcheng,Long, Wenhao,Wan, Xiaobing,Zheng, Yonggao
supporting information, p. 23603 - 23608 (2020/10/29)
This work demonstrates photoredox vicinal dichlorination of alkenes, based on the homolysis of CuCl2 in response to irradiation with visible light. This catalysis proceeds via a ligand to metal charge transfer process and provides an exciting opportunity for the synthesis of 1,2-dichloride compounds using an inexpensive, low-molecular-weight chlorine source. This new process exhibits a wide substrate scope, excellent functional group tolerance, extraordinarily mild conditions and does not require external ligands. Mechanistic studies show that the ready formation of chlorine atom radicals is responsible for the facile formation of C?Cl bonds in this synthetic process.
NMP-mediated chlorination of aliphatic alcohols with aryl sulfonyl chloride for the synthesis of alkyl chlorides
Zheng, Dagui,Mao, Liu-Liang,Zhu, Xian-Hong,Zhou, An-Xi
supporting information, p. 2793 - 2800 (2018/11/06)
NMP-mediated chlorination of aliphatic alcohols has been developed for the synthesis of alkyl chlorides. This facile, efficient and practical approach used simple and readily available aryl sulfonyl chlorides as the chlorination reagent for the construction of C–Cl bond in good to excellent yields with mild conditions and broad substrate scope.
Halogenation through Deoxygenation of Alcohols and Aldehydes
Chen, Jia,Lin, Jin-Hong,Xiao, Ji-Chang
supporting information, p. 3061 - 3064 (2018/05/28)
An efficient reagent system, Ph3P/XCH2CH2X (X = Cl, Br, or I), was very effective for the deoxygenative halogenation (including fluorination) of alcohols (including tertiary alcohols) and aldehydes. The easily available 1,2-dihaloethanes were used as key reagents and halogen sources. The use of (EtO)3P instead of Ph3P could also realize deoxy-halogenation, allowing for a convenient purification process, as the byproduct (EtO)3Pa?O could be removed by aqueous washing. The mild reaction conditions, wide substrate scope, and wide availability of 1,2-dihaloethanes make this protocol attractive for the synthesis of halogenated compounds.
Mild Aliphatic and Benzylic Hydrocarbon C-H Bond Chlorination Using Trichloroisocyanuric Acid
Combe, Sascha H.,Hosseini, Abolfazl,Parra, Alejandro,Schreiner, Peter R.
, p. 2407 - 2413 (2017/03/11)
We present the controlled monochlorination of aliphatic and benzylic hydrocarbons with only 1 equiv of substrate at 25-30 °C using N-hydroxyphthalimide (NHPI) as radical initiator and commercially available trichloroisocyanuric acid (TCCA) as the chlorine source. Catalytic amounts of CBr4 reduced the reaction times considerably due to the formation of chain-carrying ·CBr3 radicals. Benzylic C-H chlorination affords moderate to good yields for arenes carrying electron-withdrawing (50-85%) or weakly electron-donating groups (31-73%); cyclic aliphatic substrates provide low yields (24-38%). The products could be synthesized on a gram scale followed by simple purification via distillation. We report the first direct side-chain chlorination of 3-methylbenzoate affording methyl 3-(chloromethyl)benzoate, which is an important building block for the synthesis of vasodilator taprostene.
Direct halogenation of alcohols with halosilanes under catalyst- and organic solvent-free reaction conditions
Ajvazi, Njomza,Stavber, Stojan
supporting information, p. 2430 - 2433 (2016/05/19)
A chemoselective method for the direct halogenation of different types of alcohols with halosilanes under catalyst- and solvent-free reaction conditions (SFRC) is reported. Various primary, secondary and tertiary benzyl alcohols and tertiary alkyl alcohols were directly transformed to the corresponding benzyl and alkyl halides, respectively, using chlorotrimethylsilane (TMSCl) and bromotrimethylsilane (TMSBr).
Microwave assisted solid additive effects in simple dry chlorination reactions with n-chlorosuccinimide
Bucos, Madalina,Villalonga-Barber, Carolina,Micha-Screttas, Maria,Steele, Barry R.,Screttas, Constantinos G.,Heropoulos, Georgios A.
experimental part, p. 2061 - 2065 (2010/04/26)
Solid additives participate in the dry microwave assisted chlorination reaction of N-chlorosuccinimide with the xylenes affecting both yields and chemoselectivities. Total yields can be increased up to nine times for simple alkylaromatics and chemoselectivities can be altered according to the desired ring or α-side chlorination product by choosing the appropriate additive. We believe that in these reactions the solid additives play a very important role by increasing yields and affecting chemoselectivities, as well as behaving as microwave energy absorbers that consequently aid the transfer of heat to the active reagents.
Design, synthesis, and antitumor activity of new bis-aminomethylnaphthalenes
Bollini, Mariela,Casal, Juan Jose,Bruno, Ana Maria
, p. 8003 - 8010 (2008/12/23)
A new series of bis-aminomethylnaphthalenes were synthesized in satisfactory overall yield, through a simple synthetic strategy using reductive amination. The DNA binding properties of these compounds have been examined and compared to those of reference drugs using an UV spectroscopy method. The compounds were evaluated for their in vitro anticancer activity and some of them were studied in vivo. Compound 15 exhibited remarkable antitumor activity and represents a novel template for anticancer chemotherapy and can serve as a new lead compound.
Double elimination protocol for the synthesis of arylene ethynylenes containing heteroaromatic rings
Orita, Akihiro,Ye, Fangguo,Babu, Govindarajulu,Ikemoto, Tomohiro,Otera, Junzo
, p. 716 - 727 (2007/10/03)
The double elimination reaction of β-substituted sulfones offers a versatile strategy for synthesis of arylene ethynylene kits containing heteroaromatic rings. A sequence of aldol reaction between α-sulfonyl carbanion and aldehyde, trapping the resulting aldolate to give β-substituted sulfone, and double elimination of this intermediate can be integrated in one pot. This protocol allows thiophene, pyridine, and ferrocene units to be accommodated in phenylene ethynylene arrays.
Design, synthesis, and structure-activity relationships of haloenol lactones: Site-directed and isozyme-selective glutathione S-transferase inhibitors
Wu, Zhixing,Minhas, Gurpreet Singh,Wen, Dingyi,Jiang, Hualiang,Chen, Kaixian,Zimniak, Piotr,Zheng, Jiang
, p. 3282 - 3294 (2007/10/03)
Overexpression of glutathione S-transferase (GST), particularly the GST-π isozyme, has been proposed to be one of the biochemical mechanisms responsible for drug resistance in cancer chemotherapy, and inhibition of overexpressed GST has been suggested as an approach to combat GST-induced drug resistance. 3-Cinnamyl-5(E)-bromomethylidenetetrahydro-2-furanone (1a), a lead compound of site-directed GST-π inactivator, has been shown to potentiate the cytotoxic effect of cisplatin on tumor cells. As an initial step to develop more potent and more selective haloenol lactone inactivators of GST-π, we examined the relationship between the chemical structures of haloenol lactone derivatives and their GST inhibitory activity. A total of 16 haloenol lactone derivatives were synthesized to probe the effects of (1) halogen electronegativity, (2) electron density of aromatic rings, (3) molecular size and rigidity, (4) lipophilicity, and (5) aromaticity on the potency of GST-π inactivation. The inhibitory potency of each compound was determined by time-dependent inhibition tests, and recombinant human GST-π was used to determine their inhibitory activity. Our structure-activity relationship studies demonstrated that (1) reactivity of the halide leaving group plays a weak role in GST inactivation by the haloenol lactones, (2) aromatic electron density may have some influence on the potency of GST inactivation, (3) high rigidity likely disfavors enzyme inhibition, (4) lipophilicity is inversely proportional to enzyme inactivation, and (5) an unsaturated system may be important for enzyme inhibition. This work facilitated understanding of the interaction of GST-π with haloenol lactone derivatives as site-directed and isozyme-selective inactivators, possibly potentiating cancer chemotherapy.
C17,20-lyase inhibitors I. Structure-based de novo design and SAR study of C17,20-lyase inhibitors.
Matsunaga, Nobuyuki,Kaku, Tomohiro,Itoh, Fumio,Tanaka, Toshimasa,Hara, Takahito,Miki, Hiroshi,Iwasaki, Masahiko,Aono, Tetsuya,Yamaoka, Masuo,Kusaka, Masami,Tasaka, Akihiro
, p. 2251 - 2273 (2007/10/03)
Novel nonsteroidal C(17,20)-lyase inhibitors were synthesized using de novo design based on its substrate, 17 alpha-hydroxypregnenolone, and several compounds exhibited potent C(17,20)-lyase inhibition. However, in vivo activities were found to be short-lasting, and in order to improve the duration of action, a series of benzothiophene derivatives were evaluated. As a result, compounds 9h, (S)-9i, and 9k with nanomolar enzyme inhibition (IC(50)=4-9 nM) and 9e (IC(50)=27 nM) were identified to have powerful in vivo efficacy with extended duration of action. The key structural determinants for the in vivo efficacy were demonstrated to be the 5-fluoro group on the benzothiophene ring and the 4-imidazolyl moiety. Superimposition of 9k and 17 alpha-hydroxypregnenolone demonstrated their structural similarity and enabled rationalization of the pharmacological results. In addition, selected compounds were also identified to be potent inhibitors of human enzyme with IC(50) values of 20-30 nM.
