3469-06-5Relevant articles and documents
Photochemical Decomposition of Benzocyclobutenone p-Toluenesulfonylhydrazone
Frimer, Aryeh,Weiss, Joseph,Rosental, Zilpa
, p. 2516 - 2522 (1994)
The photochemical decomposition of benzocyclobutenone p-toluenesulfonylhydrazone led to a wide variety of products including the E- and Z-isomers of 1,1'-bi(benzocyclobutenylidene) 6a; cis-trans-benzocyclobutenylidene trimer 7; cyclohepatrienes 8-10; benzocyclobutenone azine in it's anti-anti(11), anti-syn (12), and syn-syn conformations (13); anti- and syn-benzocyclobutenone N-benzocyclobutenyl-N-tosylhydrazone (14 and 15, respectively); (benzocyclobutenyl)hydrazine (16); benzocyclobutenyl p-tolyl sulfone (17); and benzocyclobutenone 1.Their isolation, identification and mechanism of formation are discussed.The data indicate that while the addition of arylcarbenes to alkenes results in the preferential formation of the more-hindered syn products, arylcarbene 5 adds to aryl olefins (styrenes and dimer 6) in a stereospecific anti orientation to give the less-hindered product.In addition, the minimal steric effects observed in these systems presumably results from the 90 deg angle of the cyclobutyl ring, which pulls the phenyl ring back and thus minimizes its steric contribution.
A very short synthesis of steroids from 1,3-butadiene and benzocyclobutenes
Michellys,Maurin,Toupet,Pellissier,Santelli
, p. 115 - 122 (2001)
Lewis acid mediated addition of 1,8-bis(trimethylsilyl)octa-2,6-diene (BISTRO) 1 to succinic anhydride led to spirolactone 2 [(±)-6,9-divinyl-1-oxaspiro[4.4]nonan-2-one]. Methoxycarbonylation followed by stereoselective alkylation by various benzocyclobutenes afforded the substituted benzocyclobutene steroid precursors 5. Thermolysis of 5 gave rise to steroids (±)-6 with a transanti-cis configuration in five steps and in a highly stereoselective manner. Modifications of the sequence allowed the preparation of steroids (±)-11 with trans-anti-trans configuration.
Catalytic Asymmetric Homologation of Ketones with α-Alkyl α-Diazo Esters
Tan, Fei,Pu, Maoping,He, Jun,Li, Jinzhao,Yang, Jian,Dong, Shunxi,Liu, Xiaohua,Wu, Yun-Dong,Feng, Xiaoming
supporting information, p. 2394 - 2402 (2021/02/16)
The homologation of ketones with diazo compounds is a useful strategy to synthesize one-carbon chain-extended acyclic ketones or ring-expanded cyclic ketones. However, the asymmetric homologation of acyclic ketones with α-diazo esters remains a challenge due to the lower reactivity and complicated selectivity. Herein, we report the enantioselective catalytic homologation of acetophenone and related derivatives with α-alkyl α-diazo esters utilizing a chiral scandium(III) N,N′-dioxide as the Lewis acid catalyst. This reaction supplies a highly chemo-, regio-, and enantioselective pathway for the synthesis of optically active β-keto esters with an all-carbon quaternary center through highly selective alkyl-group migration of the ketones. Moreover, the ring expansion of cyclic ketones was accomplished under slightly modified conditions, affording a series of enantioenriched cyclic β-keto esters. Density functional theory calculations have been carried out to elucidate the reaction pathway and possible working models that can explain the observed regio- and enantioselectivity.
Synthetic approach to benzocyclobutenones using visible light and a phosphonate auxiliary
Yano, Takaaki,Kawasaki, Tairin,Yuhki, Tatsuya,Ishida, Naoki,Murakami, Masahiro
supporting information, p. 1224 - 1227 (2018/02/23)
Reported herein is a two-step procedure to synthesize benzocyclobutenones from (o-alkylbenzoyl)phosphonates. It consists of a visible-light-driven cyclization reaction forming phosphonate-substituted benzocyclobutenols and subsequent elimination reaction of the H-phosphonate, which assumes a key role as the recyclable auxiliary. A wide variety of functionalized benzocyclobutenones, which include those difficult to synthesize by conventional methods, are efficiently synthesized.
1-Aminobenzocyclobutene-1-phosphonic Acid and Related Compounds as Inhibitors of Phenylalanine Ammonia-Lyase
Zoń, Jerzy,Miziak, Piotr
, (2017/05/17)
Five new geminal aminocycloalkanephosphonic acids (4 – 8) containing both an aromatic ring and a cycloalkane ring were synthesized and evaluated as potential inhibitors of buckwheat phenylalanine ammonia-lyase (PAL). Within the set of compounds which are related to 2-aminoindane-2-phosphonic acid (AIP, 3), a known powerful inhibitor of PAL, racemic 1-aminobenzocyclobutene-1-phosphonic acid (4), was six times weaker than AIP as an in vitro inhibitor of buckwheat PAL, but six times stronger than AIP as an in vivo inhibitor of phenylalanine-derived anthocyanin synthesis in buckwheat.
Synthesis of a polymerizable benzocyclobutene that undergoes ring-opening isomerization at reduced temperature
Pugh, Coleen,Baker, James S.,Storms, William K.
supporting information, p. 148 - 152 (2014/01/06)
1-Ethoxyvinylbenzocyclobutene is a substituted benzocyclobutene that undergoes radical polymerization to produce polymers that can be crosslinked at 100-150 °C. The 4- and 5-vinyl isomers are synthesized in a 1:4 ratio via a halogenated benzyne intermediate produced from anthranilic acid, followed by cycloaddition with ethyl vinyl ether and replacement of the halogen atom with a vinyl group. Georg Thieme Verlag Stuttgart · New York.
Design and synthesis of conformationally constrained analogues of cis-cinnamic acid and evaluation of their plant growth inhibitory activity
Nishikawa, Keisuke,Fukuda, Hiroshi,Abe, Masato,Nakanishi, Kazunari,Tazawa, Yuta,Yamaguchi, Chihiro,Hiradate, Syuntaro,Fujii, Yoshiharu,Okuda, Katsuhiro,Shindo, Mitsuru
, p. 223 - 234 (2014/01/06)
1-O-cis-Cinnamoyl-β-d-glucopyranose is known to be one of the most potent allelochemical candidates and was isolated from Spiraea thunbergii Sieb by Hiradate et al. (2004), who suggested that it derived its strong inhibitory activity from cis-cinnamic acid, which is crucial for phytotoxicity. In this study, key structural features and substituent effects of cis-cinnamic acid (cis-CA) on lettuce root growth inhibition was investigated. These structure-activity relationship studies indicated the importance of the spatial relationship of the aromatic ring and carboxylic acid moieties. In this context, conformationally constrained cis-CA analogues, in which the aromatic ring and cis-olefin were connected by a carbon bridge, were designed, synthesized, and evaluated as plant growth inhibitors. The results of the present study demonstrated that the inhibitory activities of the five-membered and six-membered bridged compounds were enhanced, up to 0.27 μM, and were ten times higher than cis-CA, while the potency of the other compounds was reduced.
Enzymatic Baeyer-Villiger oxidation of Benzo-Fused ketones: Formation of regiocomplementary lactones
Rioz-Martinez, Ana,De Gonzalo,Torres Pazmino, Daniel E.,Fraaije, Marco W.,Gotor, Vicente
experimental part, p. 2526 - 2532 (2009/09/25)
Baeyer-Villiger monooxygenases (BVMOs) are enzymes that are known to catalyse the Baeyer-Villiger oxidation of ketones in aqueous media using O2 as oxidant. Herein, we describe the oxidation of a set of diverse benzo-fused ketones by three different BVMOs
DENDRITIC MOLECULAR INTRACELLULAR TRANSPORTERS AND METHODS OF MAKING AND USING SAME
-
Page/Page column 104, (2010/11/30)
In accordance with the purpose(s) of the invention, as embodied and broadly described herein, the invention, in one aspect, relates to compounds comprising the structure: and at least one guanidinium residue, wherein m is zero or a positive integer. Also disclosed are methods of preparing the disclosed compounds. Also disclosed are methods of intracellular delivery comprising administering the disclosed compounds and compositions to a subject. Also disclosed are pharmaceutical compositions comprising a therapeutically effective amount of one or more compounds or compositions of the invention and a pharmaceutically acceptable carrier. This abstract is intended as a scanning tool for purposes of searching in the particular art and is not intended to be limiting of the present invention.
The elusive benzocyclobutenylidene: A combined computational and experimental attempt
Nicolaides,Matsushita,Yonezawa,Sawai,Tomioka,Stracener,Hodges,McMahon
, p. 2870 - 2876 (2007/10/03)
Ab initio and density functional theory calculations predict that benzocyclobutenylidene (1) has a singlet ground state in contrast to the parent phenylcarbene and many other simply substituted arylcarbenes. Calculations also predict that 1 should lie in a relatively deep potential well, while its triplet state is 14.5 kcal mol-1 higher in energy. However, attempts to observe 1 directly by photolysis of two different nitrogenous precursors were not successful. Irradiation of diazobenzocyclobutene (7) (λ > 534 nm or λ > 300 nm) or azibenzocyclobutene (10) (λ > 328 nm) in Ar matrixes at 10 K leads to the formation of the strained cycloalkyne 7-methylenecyclohepta-3,5-dien-1-yne (3). 13C-Labeled 3 was also prepared in a similar manner. There is very good agreement between experimental IR spectra and computationally derived harmonic vibrational frequencies for 3 and [13C]-3 and excellent agreement between observed and calculated isotopic shifts. Prolonged short-wavelength irradiation converts 3 into benzocyclobutadiene (5). Phenylacetylene (6) and benzocyclobutadiene dimer (11) were identified as products arising from flash vacuum pyrolysis of diazirine 10 at 500 °C.
