17497-53-9Relevant articles and documents
2(S)-(Cycloalk-1-enecarbonyl)-1-(4-phenyl-butanoyl)pyrrolidines and 2(S)-(aroyl)-1-(4-phenylbutanoyl)pyrrolidines as prolyl oligopeptidase inhibitors
Jarho, Elina M.,Venaelaeinen, Jarkko I.,Poutiainen, Sami,Leskinen, Harri,Vepsaelaeinen, Jouko,Christiaans, Johannes A.M.,Forsberg, Markus M.,Maennistoe, Pekka T.,Wallen, Erik A.A.
, p. 2024 - 2031 (2007)
In order to replace the P2-P1 amide group, different 1-cycloalkenyls and 2-aryls were studied in the place of the P1 pyrrolidine group of a 4-phenylbutanoyl-l-Pro-pyrrolidine structure, which is a well-known prolyl oligopeptidase inhibitor SUAM-1221. The
Copper-Catalyzed C?P Cross-Coupling of (Cyclo)alkenyl/Aryl Bromides and Secondary Phosphine Oxides with in situ Halogen Exchange
Stankevi?, Marek,Wo?nicki, Pawe?
, p. 3484 - 3491 (2021/07/22)
An efficient protocol for concurrent tandem halogen exchange/C?P cross-coupling of cycloalkenyl bromides and secondary phosphine oxides has been developed. The catalytic system is based on cheap and air-stable copper(I) iodide as the precatalyst, commercially available N,N’-dimethylethylenediamine as the ligand, and Cs2CO3 or K2CO3 as the base. The use of sodium iodide as an additive reduces the excessive use of organic bromides to near-stoichiometric by promoting the in situ transformation to the corresponding iodides. Diarylphosphine oxides undergo cycloalkenylation with 35–99 % yields and dicyclohexylphosphine oxide with 30–53 % yields. In the case of acyclic alkenyl bromides the cross-coupling products undergo conjugate addition of diphenylphosphine oxide and satisfying yields are observed only for internal olefins. In the case of aryl bromides satisfying yields (43–72 %) are observed only for sterically unhindered arenes or arenes possessing an ortho-directing group. Cycloalkenylphosphine oxides prepared in the cross-coupling reaction undergo base-catalyzed and base-promoted conjugate addition to give bis(phosphinoyl)cycloalkanes.
Amino- and azidocarbonylation of iodoalkenes
Mikle, Gábor,Skoda-F?ldes, Rita,Kollár, László
, (2021/10/14)
Iodoalkenes, available from ketones via their hydrazones, underwent palladium-catalysed azidocarbonylation. Depending on the structure of the acyl azides, consecutive hydrolysis toward corresponding primary amides was observed. ‘Direct’ aminocarbonylation
Stereoselective Csp3?Csp2 Cross-Couplings of Chiral Secondary Alkylzinc Reagents with Alkenyl and Aryl Halides
Skotnitzki, Juri,Kremsmair, Alexander,Keefer, Daniel,Gong, Ye,de Vivie-Riedle, Regina,Knochel, Paul
, p. 320 - 324 (2019/11/26)
We report palladium-catalyzed cross-coupling reactions of chiral secondary non-stabilized dialkylzinc reagents, prepared from readily available chiral secondary alkyl iodides, with alkenyl and aryl halides. This method provides α-chiral alkenes and arenes with very high retention of configuration (dr up to 98:2) and satisfactory overall yields (up to 76 % for 3 reaction steps). The configurational stability of these chiral non-stabilized dialkylzinc reagents was determined and exceeded several hours at 25 °C. DFT calculations were performed to rationalize the stereoretention during the catalytic cycle. Furthermore, the cross-coupling reaction was applied in an efficient total synthesis of the sesquiterpenes (S)- and (R)-curcumene with control of the absolute stereochemistry.
Sequential Suzuki-Miyaura Coupling/Lewis Acid-Catalyzed Cyclization: An Entry to Functionalized Cycloalkane-Fused Naphthalenes
Mahecha-Mahecha, Camilo,Lecornué, Frédéric,Akinari, Sumita,Charote, Thomas,Gamba-Sánchez, Diego,Ohwada, Tomohiko,Thibaudeau, Sébastien
, p. 6267 - 6271 (2020/09/02)
Functionalized angular cycloalkane-fused naphthalenes were prepared using a two-step process involving a Pd-catalyzed Suzuki-Miyaura coupling of aryl pinacol boronates and vinyl triflates followed by a boron trifluoride etherate-catalyzed cycloaromatization.
Regioselective Synthesis of Vinyl Halides, Vinyl Sulfones, and Alkynes: A Tandem Intermolecular Nucleophilic and Electrophilic Vinylation of Tosylhydrazones
Ojha, Devi Prasan,Prabhu, Kandikere Ramaiah
, p. 18 - 21 (2015/07/28)
A diazo species is trapped in an intermolecular fashion by two independent ion species in tandem at the carbene center to install an electrophile and a nucleophile on the same carbon. This metal-free concept, which is unprecedented, has been illustrated by regioselective synthesis of a variety of vinyl halides, vinyl sulfones, and alkyne derivatives. (Chemical Equation Presented).
Synthesis and photochemistry of 1-iodocyclohexene: Influence of ultrasound on ionic vs. radical behaviour
Blaskovicova, Marika,Gaplovsky, Anton,Blasko, Jaroslav
, p. 188 - 193 (2007/10/03)
Simultaneous application of UV light and ultrasonic irradiation to a reaction mixture containing 1-iodocyclohexene is reported. The irradiation of 1-iodocyclohexene in methanol was carried out with or without addition of zinc. The effect of ultrasound or mechanical stirring on this solid-liquid system was also compared. The irradiation of 1-iodocyclohexene in methanol in the presence of zinc increases the yield of the nucleophilic trapping product, compared with the yield after irradiation in the absence of zinc. The photodegradation of 1-iodocyclohexene was slightly accelerated after addition of zinc. A rapid formation of radical product was accompanied by substantial decrease of 1-iodocyclohexene after application of ultrasound and irradiation without the zinc. The ultrasound significantly affects the photobehaviour of this reaction, predominantly its radical route. The joint application of ultrasound and zinc contributes positively to the production of radical and ionic products. The sonochemical stirring is more effective than mechanical stirring.
Michael addition-elimination mechanism for nucleophilic substitution reaction of cycloalkenyl iodonium salts and selectivity of 1,2-hydrogen shift in cycloalkylidene intermediate
Fujita, Morifumi,Wan, Hyeok Kim,Fujiwara, Koji,Okuyama, Tadashi
, p. 480 - 488 (2007/10/03)
(Chemical Equation Presented) Reactions of cyclohexenyl and cyclopentenyl iodonium salts with cyanide ion in chloroform give cyanide substitution products of allylic and vinylic forms. Deuterium-labeling experiments show that the allylic product is formed via the Michael addition of cyanide to the vinylic iodonium salt, followed by elimination of the iodonio group and 1,2-hydrogen shift in the 2-cyanocycloalkylidene intermediate. The hydrogen shift preferentially occurs from the methylene rather than the methine β-position of the carbene, and the selectivity is rationalized by the DFT calculations. The Michael reaction was also observed in the reaction of cyclopentenyliodonium salt with acetate ion in chloroform. The vinylic substitution products are ascribed to the ligand-coupling (via λ3-iodane) and elimination-addition (via cyclohexyne) pathways.
From vinyl sulfides, sulfoxides and sulfones to vinyl zirconocene derivatives
Farhat, Shahera,Zouev, Irena,Marek, Ilan
, p. 1329 - 1337 (2007/10/03)
An easy and straightforward new method for the preparation of sp 2 zirconocene derivatives from a wide range of heterosubstituted alkenes such as vinyl sulfides, sulfoxides and sulfones is described. In all cases, a complete isomerization of the stereochemistry is observed and only the E-isomer is obtained. The reactivity of the resulting vinylic organometallic can be increased by a transmetalation reaction into organocopper, organozinc or organopalladium species and, therefore, several carbon-carbon formation were easily realized.
Michael addition of cyanide to cyclohex-1-enyliodonium salts
Fujita, Morifumi,Kim, Wan Hyeok,Okuyama, Tadashi
, p. 382 - 383 (2007/10/03)
Reaction of 4-substituted cyclohex-1-enyliodonium salt with cyanide in chloroform produces three isomeric cyanocyclohexenes, ipso and two cine products. Deuterium labeling experiments showed that the allylic cine product is formed via the Michael addition of cyanide, followed by elimination of the iodonio group and a 1,2-H shift.
