124306-12-3Relevant academic research and scientific papers
Total synthesis of cryptomoscatones D1 and D2: Stereochemical assignment of cryptomoscatone D1
Toneto Novaes, Luiz Fernando,Drekener, Roberta Lopes,Avila, Carolina Martins,Pilli, Ronaldo Aloise
, p. 6467 - 6473 (2014)
The first total synthesis and structural elucidation of cryptomoscatone D1, and a novel synthetic approach for cryptomoscatone D2 were achieved in 30% and 29% overall yield, respectively. The synthesis relied on the use of a key Mukaiyama aldol reaction followed by a diastereoselective carbonyl reduction that allowed the preparation of four cryptomoscatone isomers in a stereochemically divergent manner. Comparison of NMR data and CD curves of the synthetic stereoisomers and natural products confirmed the stereochemical nature of cryptomoscatone D2, and led to establishing the absolute configuration of cryptomoscatone D1.
Two-Step Synthesis of (γ,γ-Difluoroallyl)carbonyl Compounds via Addition of 1,1,2-Trichloro-2,2-difluoroethyl Radical to Silyl Enol Ethers Followed by Reductive Dechlorination
Okano, Takashi,Shimizu, Toshihiro,Sumida, Koji,Eguchi, Shoji
, p. 5163 - 5166 (1993)
Ru(II)- or Cu(I)-induced radical reaction of CF2ClCCl2. radical (2), regioselectively derived from CF2ClCCl3, to trimethylsilyl enol ethers and a ketene silyl acetal yields (β,β,γ-trichloro-γ,γ-difluoropropyl)carbonyl compounds 5 as the intermediates.Spontaneous dehydrochlorination affords carbonyl compounds 4.Reductive dechlorination of 4 with zinc gave γ,γ-difluoroallyl ketones 7a-e and an ester 7f.In some cases, Ni(0)-catalyzed reduction with zinc is superior than the simple hydrodechlorination.
Diastereoselective synthesis of five- and seven-membered rings by [2+2+1], [3+2], [3+2+2], and [4+3] carbocyclization reactions of β-substituted (alkenyl)(methoxy)carbene complexes with methyl ketone lithium enolates
Barluenga, Jose,Alonso, Jorge,Fananas, Francisco J.
, p. 4995 - 5006 (2005)
β-Substituted alkenylcarbene complexes react with methyl ketone lithium etiolates to give different carbocyclization products depending on the structure of the lithium enolate, on the metal of the carbene complex, and on the reaction media. Thus, the reac
Ni-Catalyzed β-Alkylation of Cyclopropanol-Derived Homoenolates
Mills, L. Reginald,Zhou, Cuihan,Fung, Emily,Rousseaux, Sophie A. L.
supporting information, p. 8805 - 8809 (2019/11/03)
Metal homoenolates are valuable synthetic intermediates which provide access to β-functionalized ketones. In this report, we disclose a Ni-catalyzed β-alkylation reaction of cyclopropanol-derived homoenolates using redox-active N-hydroxyphthalimide (NHPI) esters as the alkylating reagents. The reaction is compatible with 1°, 2°, and 3° NHPI esters. Mechanistic studies imply radical activation of the NHPI ester and 2e β-carbon elimination occurring on the cyclopropanol.
Synthesis of 1-hydrocarbon substituted cyclopropyl silyl ketones
Honda, Mitsunori,Sasaki, Sho,Nishimoto, Tsuyoshi,Koshiro, Hiromoto,Kunimoto, Ko-Ki,Segi, Masahito
, p. 3777 - 3781 (2018/09/21)
The synthesis of cyclopropyl silyl ketones possessing a hydrocarbon group at 1-position of three-membered ring was investigated. The reaction of sulfoxonium ylide with α,β-unsaturated acylsilanes derived from α,β-unsaturated aldehydes did not afford the desired acylsilane derivatives. Instead, the corresponding silyl enol ethers were yielded exclusively. On the other hand, the Corey-Chaykovsky cyclopropanation of α-substituted α,β-unsaturated aldehydes proceeded well to give 1-substituted cyclopropyl aldehydes. The silyl substitution of formyl proton in the obtained aldehydes via umpolung of carbonyl group afforded the target acylsilanes.
Highly Enantioselective [5 + 2] Annulations through Cooperative N-Heterocyclic Carbene (NHC) Organocatalysis and Palladium Catalysis
Singha, Santanu,Patra, Tuhin,Daniliuc, Constantin G.,Glorius, Frank
supporting information, p. 3551 - 3554 (2018/03/21)
The highly enantioselective [5 + 2] annulation of enals with vinylethylene carbonates through a cooperative N-heterocyclic carbene (NHC)/Pd catalytic system is reported. The use of a bidentate phosphine ligand was crucial to prevent coordination of the NH
Novel Benzo[a]quinolizidine Analogs Induce Cancer Cell Death through Paraptosis and Apoptosis
Zheng, Hongbo,Dong, Yiwen,Li, Lin,Sun, Bin,Liu, Lei,Yuan, Huiqing,Lou, Hongxiang
, p. 5063 - 5076 (2016/06/13)
Paraptosis is nonapoptotic cell death characterized by massive endoplasmic reticulum (ER)- or mitochondria-derived vacuoles. Induction of paraptosis offers significant advantages for the treatment of chemotherapy-resistant tumors compared with anticancer drugs that rely on apoptosis. Because some natural alkaloids induce paraptotic cell death, a novel series of benzo[a]quinolizidine derivatives were synthesized, and their antiproliferative activity and ability to induce cytoplasmic vacuolation were analyzed. Structural optimization led to the identification of the potent compound 22b, which inhibited cancer cell proliferation in vitro and in vivo and profoundly facilitated paraptosis-like cell death and induced caspase-dependent apoptosis. Further investigation revealed that 22b-mediated vacuolation originated from persistent ER stress and upregulation of LC3B. Paraptosis induced by benzo[a]quinolizidine derivatives thus represents an alternative strategy for cancer chemotherapy.
Synthesis of β-Amino-Substituted Enones by Addition of Substituted Methyl Enones to Sulfinimines: Application to the Total Synthesis of Alkaloids (+)-Lasubine II and (+)-241D and the Formal Total Synthesis of (-)-Lasubine i
Reddy, Arava Amaranadha,Reddy, Polimera Obula,Prasad, Kavirayani R.
, p. 11363 - 11371 (2016/11/29)
Addition of silyl enol ethers obtained from substituted methyl enones to chiral sulfinimines afforded the β-amino-substituted enones with excellent selectivity. Utility of the obtained N-sulfinyl β-amino ketones possessing α,β-unsaturation is exemplified
Conversion of Simple Cyclohexanones into Catechols
Liang, Yu-Feng,Li, Xinyao,Wang, Xiaoyang,Zou, Miancheng,Tang, Conghui,Liang, Yujie,Song, Song,Jiao, Ning
supporting information, p. 12271 - 12277 (2016/09/28)
A novel I2-catalyzed direct conversion of cyclohexanones to substituted catechols under mild and simple conditions has been described. This novel transformation is remarkable with the multiple oxygenation and dehydrogenative aromatization processes enabled just by using DMSO as the solvent, oxidant, and oxygen source. This metal-free and simple system demonstrates a versatile protocol for the synthesis of highly valuable substituted catechols and therefore streamlines the synthesis and modification of biologically important molecules for drug discovery.
Stereoselective Synthesis of Highly Substituted Tetrahydrofurans through Diverted Carbene O-H Insertion Reaction
Nicolle, Simon M.,Lewis, William,Hayes, Christopher J.,Moody, Christopher J.
supporting information, p. 8485 - 8489 (2015/11/27)
Copper- or rhodium-catalyzed reactions of diazocarbonyl compounds with β-hydroxyketones give highly substituted tetrahydrofurans with excellent diastereoselectivity. Under mild conditions, the single-step process starts as a carbene O-H insertion reaction, but is diverted by an intramolecular aldol reaction. Gone astray: Copper- or rhodium-catalyzed reactions of diazocarbonyl compounds with β-hydroxyketones give highly substituted tetrahydrofurans with excellent diastereoselectivity. The single-step reaction proceeds under mild conditions, starting as a carbene O-H insertion reaction, but then diverting to an intramolecular aldol reaction.
