13837-45-1Relevant academic research and scientific papers
Synthesis, Purification, and Rotational Spectroscopy of (Cyanomethylene)Cyclopropane—An Isomer of Pyridine
Esselman, Brian J.,Kougias, Samuel M.,Zdanovskaia, Maria A.,Woods, R. Claude,McMahon, Robert J.
, p. 5601 - 5614 (2021)
The gas-phase rotational spectrum of (cyanomethylene)cyclopropane, (CH2)2C═CHCN, generated by a Wittig reaction between the hemiketal of cyclopropanone and (cyanomethylene)triphenylphosphorane, is presented for the first time. This small, highly polar nitrile is a cyclopropyl-containing structural isomer of pyridine. The rotational spectra of the ground state and two vibrationally excited states were observed, analyzed, and least-squares fit from 130 to 360 GHz. Over 3900 R-, P-, and Q-branch, ground-state rotational transitions were fit to low-error, partial octic, A- and S-reduced Hamiltonians, providing precise determinations of the spectroscopic constants. The two lowest-energy vibrationally excited states, ν17and ν27, form a Coriolis-coupled dyad displaying smalla- andb-type resonances. Transitions for these two states were measured and least-squares fit to a two-state, partial octic, A-reduced Hamiltonian in the Irrepresentation with nine Coriolis-coupling terms (Ga,GaJ,GaK,GaJJ,Fbc,FbcJ,FbcK,Gb, andGbJ). The observation of many resonant transitions and nine nominal interstate transitions enabled a very accurate and precise energy difference between ν17and ν27to be determined: ΔE17,27= 29.8975453 (33) cm-1. The spectroscopic constants presented herein provide the foundation for future astronomical searches for (cyanomethylene)cyclopropane.
Cyanomethylene cyclopropane, a useful dipolarophile and dienophile in [2+3] and [2+4] cycloadditions
Mauduit, Marc,Kouklovsky, Cyrille,Langlois, Yves
, p. 6857 - 6860 (1998)
Cyanomethylene cyclopropane, prepared for the first time on large scale proved to be a reactive dipolarophile and dienophile in several cycloadditions. The reactivity of this compound has been compared with 3- methyl-2-butenenitrile, ethyl 3-methyl-2-butenoate and ethoxycarbonylmethylene cyclopropane.
Experimental and Computational Studies on Rh(I)-Catalyzed Reaction of Siloxyvinylcyclopropanes and Diazoesters
Feng, Sheng,Wang, Kang,Ping, Yifan,Wang, Jianbo
, p. 21032 - 21039 (2020)
The Rh(I)-catalyzed reaction of siloxyvinylcyclopropanes and diazoesters leads to the formation of siloxyvinylcyclobutane and 1,4-diene derivatives. With [Rh(cod)Cl]2 as the catalyst, the formation of 1,4-diene was favored over the formation of siloxyvinylcyclobutane. By changing the catalyst to [Rh(cod)2OTf], siloxyvinylcyclobutane derivatives are formed with excellent chemoselectivities and in moderate to good yields. The alkene products are also obtained as single E configured isomers. A detailed mechanism for this transformation is proposed on the basis of mechanistic experiments and DFT calculations. The effect of catalysts on the chemoselectivity of these reactions is also examined computationally.
Stereospecific Synthesis of Enantioenriched Alkylidenecyclobutanones via Formal Vinylidene Insertion into Cyclopropanone Equivalents
Poteat, Christopher M.,Lindsay, Vincent N. G.
supporting information, p. 6482 - 6487 (2021/08/30)
1-Sulfonylcyclopropanols are employed here as efficient cyclopropanone equivalents in a formal vinylidene insertion process, providing the first general synthetic route to enantioenriched alkylidenecyclobutanones. The addition of an alkenyl-Grignard reage
Enantioselective Synthesis of Cyclopropanone Equivalents and Application to the Formation of Chiral β-Lactams
Jang, Yujin,Johnson, J. Drake,Jung, Myunggi,Lindsay, Vincent N. G.,Poteat, Christopher M.,Williams, Rachel G.
supporting information, p. 18655 - 18661 (2020/08/21)
Cyclopropanone derivatives have long been considered unsustainable synthetic intermediates because of their extreme strain and kinetic instability. Reported here is the enantioselective synthesis of 1-sulfonylcyclopropanols, as stable yet powerful equivalents of the corresponding cyclopropanone derivatives, by α-hydroxylation of sulfonylcyclopropanes using a bis(silyl) peroxide as the electrophilic oxygen source. This work constitutes the first general approach to enantioenriched cyclopropanone derivatives. Both the electronic and steric nature of the sulfonyl moiety, which serves as a base-labile protecting group and confers crystallinity to these cyclopropanone precursors, were found to have a crucial impact on the rate of equilibration to the corresponding cyclopropanone. The utility of these cyclopropanone surrogates is demonstrated in a mild and stereospecific formal [3+1] cycloaddition with simple hydroxylamines, leading to the efficient formation of chiral β-lactam derivatives.
General Synthesis of Cyclopropanols via Organometallic Addition to 1-Sulfonylcyclopropanols as Cyclopropanone Precursors
Jang, Yujin,Lindsay, Vincent N. G.,Poteat, Christopher M.,Rivera, Roger Machín
supporting information, (2020/09/02)
The addition of organometallic reagents to ketones constitutes one of the most straightforward synthetic approaches to tertiary alcohols. However, due to the absence of a well-behaved class of cyclopropanone surrogates accessible in enantioenriched form, such a trivial synthetic disconnection has received very little attention in the literature for the formation of tertiary cyclopropanols. In this work, we report a simple and high-yielding synthesis of 1-substituted cyclopropanols via the addition of diverse organometallic reagents to 1-phenylsulfonylcyclopropanols, acting here as in situ precursors of the corresponding cyclopropanones. The transformation is shown to be amenable to sp-, sp2-, or sp3-hybridized organometallic C-nucleophiles under mild conditions, and the use of enantioenriched substrates led to highly diastereoselective additions and the formation of optically active cyclopropanols.
Synthesis of Cyclopentenones with Reverse Pauson-Khand Regiocontrol via Ni-Catalyzed C-C Activation of Cyclopropanone
Jang, Yujin,Lindsay, Vincent N. G.
supporting information, p. 8872 - 8876 (2020/12/02)
A formal [3 + 2] cycloaddition between cyclopropanone and alkynes via Ni-catalyzed C-C bond activation has been developed, where 1-sulfonylcyclopropanols are employed as key precursors of cyclopropanone in the presence of trimethylaluminum. The transformation provides access to 2,3-disubstituted cyclopentenones with complete regiocontrol, favoring reverse Pauson-Khand products, where the large substituent is located at the 3-position of the ring. In the process, the trimethylaluminum additive is thought to play multiple roles, including as a Br?nsted base triggering the equilibration to cyclopropanone and liberation of methane, as well as a source of Lewis acid to activate the carbonyl group toward Ni-catalyzed C-C activation.
Last of the gem-Difluorocycloalkanes: Synthesis and Characterization of 2,2-Difluorocyclobutyl-Substituted Building Blocks
Chernykh, Anton V.,Melnykov, Kostiantyn P.,Tolmacheva, Nataliya A.,Kondratov, Ivan S.,Radchenko, Dmytro S.,Daniliuc, Constantin G.,Volochnyuk, Dmitriy M.,Ryabukhin, Sergey V.,Kuchkovska, Yuliya O.,Grygorenko, Oleksandr O.
, p. 8487 - 8496 (2019/08/30)
An efficient approach to synthesis of previously unavailable 2-substituted difluorocyclobutane building blocks was developed and applied on a multigram scale. The key step of the synthetic sequence included deoxofluorination of O-protected 2-(hydroxylmeth
COMPOUNDS FOR THE TREATMENT OF PAIN
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Paragraph 2408; 2699-2700, (2019/08/20)
Provided herein are compounds that are useful in the treatment of pain in a subject.
HPK1 INHIBITORS, PREPARATION METHOD AND APPLICATION THEREOF
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Page/Page column 151, (2019/11/12)
Disclosed are HPK-1 inhibitors having a structure represented by Formula (X), pharmaceutical compositions comprising the HPK-1 inhibitors, methods of using the HPK-1 inhibitors, such as treating cancers, methods of preparing the HPK-1 inhibitors, and the synthetic intermediates.
