5557-87-9Relevant academic research and scientific papers
Medium and Large N-Heterocycle Formation via Allene Hydroamination with a Bimetallic Rh(II) Catalyst
Bohman, Benjamin O.,Davis, Rhen C.,Forson, Kelton G.,McKnight, Caitlyn E.,Michaelis, David J.,Owens, Rachel N.,Smith, Stacey J.,Stillwell, Lillian R.,Wayment, Coriantumr Z.
supporting information, p. 63 - 68 (2022/01/19)
We report the synthesis of a 2-phosphinoimidazole-derived bimetallic Rh(II) complex that enables intramolecular allene hydroamination to form 7- to 10-member rings in high yield. Monometallic Rh complexes, in contrast, fail to achieve any product formatio
A Commercially Available and User-Friendly Catalyst for Hydroamination Reactions under Technical Conditions
Zelenay, Benjamin,Munton, Peter,Tian, Xiaojie,Díez-González, Silvia
supporting information, p. 4725 - 4730 (2019/08/01)
The activity of a simple, commercially available copper salt, [Cu(NCMe)4](BF4) in intramolecular hydroamination reactions of alkynes and allenes is presented. Reactions were successfully carried out in technical acetonitrile in the presence of air. While attempts of alkene hydroamination failed, this catalyst was also found active in intermolecular aza-Michael reactions.
Diastereoselective synthesis of pyrrolidine derivatives via a one-pot nitro-Mannich/hydroamination cascade using base and gold catalysis
?uri?, Andrej,Barber, David M.,Sanganee, Hitesh J.,Dixon, Darren J.
supporting information, p. 2777 - 2779 (2013/04/23)
An efficient one-pot nitro-Mannich/hydroamination cascade reaction for the synthesis of substituted pyrrolidines bearing three stereocentres is reported. Proceeding under the control of a combination of base and gold(i) catalysts, the cascade reaction aff
An expedient stereoselective route to the ACE tricyclic core of manzamine A via a palladium-catalysed arylative allene spirocyclisation cascade
Hawkins, Alison,Jakubec, Pavol,Ironmonger, Alan,Dixon, Darren J.
supporting information, p. 365 - 369 (2013/03/14)
Application of a novel palladium-catalysed stereoselective arylative allene spirocyclisation cascade as the key step for the construction of the ACE tricyclic core of manzamine A is described.
Highly selective cobalt-mediated [6 + 2] cycloaddition of cycloheptatriene and allenes
Clavier, Herve,Jeune, Karel Le,Riggi, Innocenzo De,Tenaglia, Alphonse,Buono, Gerard
supporting information; experimental part, p. 308 - 311 (2011/04/15)
[6 + 2] Cycloadditions between cycloheptatrienes with allenes have been investigated. Cobalt salts were found to promote this transformation efficiently. Moreover, this reaction was found to be highly selective since only one regioisomer was obtained with an excellent E/Z-selectivity.
Homoallylic amines by reductive inter- and intramolecular coupling of allenes and nitriles
Wipf, Peter,Manojlovic, Marija D.
supporting information; experimental part, p. 824 - 830 (2011/08/10)
The one-pot hydrozirconation of allenes and nitriles followed by an in situ transmetalation of the allylzirconocene with dimethylzinc or zinc chloride provides functionalized homoallylic amines. An intramolecular version of this process leads to 3-aminote
Highly efficient [2 + 2] intramolecular cyclizations of allenynes under microwave irradiation: Construction of fused bicyclic compounds
Oh, Chang Ho,Gupta, Arun Kumar,Park, Dai In,Kim, Nakjoong
, p. 5670 - 5672 (2007/10/03)
A palladium [2 + 2] cycloaddition of 1,6- and 1,7- allenyne carboxylates and microwave-mediated [2 + 2] cycloaddition of various 1,n-allenynes were developed and, particularly, the microwave irradiated [2 + 2] cycloaddition of allenynes can provide a simp
Heptafulvenone, vinylketene, butadienylketene, and allenylketene - Facile generation, observation, and radical reaction with TEMPO
Tidwell, Thomas T.,Fenwick, Michael H.
, p. 3415 - 3419 (2007/10/03)
Heptafulvenone (1), vinylketene (11), 1,3-butadienylketene [(E)-15], and allenylketene (21) have been prepared by reaction of the corresponding acyl chlorides with 1,8-bis(dimethylamino)naphthalene as long-lived species in solution at room temperature, and their ketenyl IR bands observed under these conditions for the first time, at 2101, 2118, 2111, 2117 cm-1, respectively. These unsaturated ketenes react with tetramethylpiperidinyloxyl (TEMPO, TO.) with initial attack at the carbonyl carbon giving delocalized radicals which give from 1 a mixture of the ring contracted o-, m-, and p-formylbenzoates O=CHC6H4CO2T (6) and the bis-(cycloheptatrienyl) dimer 7. The products from 11, (E)-15, and 21 are the bis(TEMPO) adducts (E,Z)-TOCH2CH= CHCO2T (12), (E,E)-TOCH2CH=CHCH=CHCO2T (17), and (E,Z)-CH2=C(OT)CH=CHCO2T (22), respectively.
Ruthenium-catalyzed two-component addition to form 1,3-dienes: Optimization, scope, applications, and mechanism
Trost,Pinkerton,Seidel
, p. 12466 - 12476 (2007/10/03)
A two component coupling of an allene and an activated olefin to form 1,3-dienes has been developed. The requisite allenes are synthesized either from terminal alkynes by a one carbon homologation using copper(I) iodide, paraformaldehyde, and diisopropyla
Spiropentylacetyl-CoA, a mechanism-based inactivator of acyl-CoA dehydrogenases
Li, Ding,Zhou, Hui-Qiang,Dakoji, Srikanth,Shin, Injae,Oh, Eugene,Liu, Hung-Wen
, p. 2008 - 2017 (2007/10/03)
Acyl-CoA dehydrogenases (ACDs) are FAD-dependent enzymes that catalyze the conversion of an appropriate fatty acyl-CoA thioester substrate to the corresponding trans-α,β-enoyl-CoA product. Early studies have shown that the de hydrogenation stereospecific and is initiated by the abstraction of the pro-R α-H, followed-by the transfer of the pro-R β-H, as a hydride equivalent, to the bound FAD. However, recent studies of the inactivation of ACDs by a metabolic of hypoglycin A, (methylenecyclopropyl)acetyl-CoA (MCPA- CoA), led to an alternative mechanism in which the reducing equivalent is delivered from the initially formed α-anion to the bound FAD via a single electron transfer process. To further explore the observed mechanistic discrepancy, we have reexamined the inhibitory properties of a closely related MCPA-CoA analogue, spiropentylacetyl-CoA (SPA-CoA), which was previously reported as a fight-binding inhibitor for ACDs. In contrast to early results, our data showed the SPA-CoA is a mechanism-based inhibitor for pig kidney medium-chain acyl-CoA dehydrogenase (MCAD) and Megasphaera elsdenii short-chain acyl-CoA dehydrogenase (SCAD) and that the inactivation is time-dependent, active-site-directed, and irreversible. More importantly, both (R)- and (S)-SPA-CoA could effectively inactivate MCAD, and the resulting inhibitor-FAD adducts appear to have one of the three-membered rings of the spiropentyl moiety cleaved. Since the inactivation is nonstereospecific with respect to C(β)-C bond scission, the ring opening of SPA-CoA leading to enzyme inactivation is likely initiated by a spiropentylcarbinyl radical. Such a radical-induced ring fragmentation is expected to be extremely facile and may bypass the chiral discrimination normally imposed by the enzyme. Thus, these results are consistent with our early notion that MCAD is capable of mediating one-electron redox chemistry. Interestingly, it was also found that (R)-SPA-CoA is an irreversible inhibitor for while the S-epimer is only a competitive inhibitor for the same enzyme. The selective inhibition exhibited by these compounds against two closely related dehydrogenases is likely a consequence of the distinct steric and electronic demands imposed by the active sites of MCAD and SCAD. Such information is important for the design of novel class-selective inhibitors to control and/or regulate fatty acid metabolism.
