66487-97-6Relevant articles and documents
SUMO INHIBITOR COMPOUNDS AND USES THEREOF
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Paragraph 0544-0546, (2020/02/23)
There are disclosed, inter alia, methods of inhibiting an E1 enzyme, and compounds useful for inhibiting an E1 enzyme.
Chemoselective Benzylation of Aldehydes Using Lewis Base Activated Boronate Nucleophiles
Hollerbach, Michael R.,Barker, Timothy J.
, p. 1425 - 1427 (2018/05/24)
A benzylation of aldehydes using primary and secondary benzylboronic acid pinacol esters is reported. Activation of the boronic ester with s-butyllithium rendered it nucleophilic toward aldehydes. The activated nucleophile chemoselectively transfers the benzyl group over the sec-butyl group, providing excellent yields of the benzylated products. 11B NMR experiments were performed to study the mechanism of this transformation.
Enantioselective 1,2-Anionotropic Rearrangement of Acylsilane through a Bisguanidinium Silicate Ion Pair
Cao, Weidi,Tan, Davin,Lee, Richmond,Tan, Choon-Hong
supporting information, p. 1952 - 1955 (2018/02/17)
Highly enantioselective bisguanidinium-catalyzed tandem rearrangements of acylsilanes are reported. The acylsilanes were activated via an addition of fluoride on the silicon to form a penta-coordinate anionic silicate intermediate. The silicate then underwent alkyl or aryl group migration from the silicon atom to the neighboring carbonyl carbon atom (1,2-anionotropic rearrangement), followed by [1,2]-Brook rearrangement to provide the secondary alcohols in high yields with excellent enantioselectivities (up to 95% ee). The isolation of an α-silylcarbinol intermediate as well as DFT calculations revealed that the 1,2-anionotropic rearrangement occurred via a bisguanidinium silicate ion pair, which is the stereodetermining step. The chiral center formed is then retained without inversion through the subsequent [1,2]-Brook rearrangement. Crotyl acylsilanes were smoothly transformed into homoallylic linear crotyl alcohols with retention of E/Z geometry, and no branched alcohols were detected. This clearly suggested that the 1,2-anionotropic rearrangement occurred through a three-membered instead of a five-membered transition state.
Bu4N+ alkoxide-initiated/autocatalytic addition reactions with organotrimethylsilanes
Das, Manas,O'Shea, Donal F.
, p. 5595 - 5607 (2014/07/08)
The use of Me3SiO-/Bu4N+ as a general activator of organotrimethylsilanes for addition reactions has been established. The broad scope of the method offers trimethylsilanes (including acetate, allyl, propargyl, benzyl, dithiane, heteroaryl, and aryl derivatives) as bench-stable organometallics that can be readily utilized as carbanion equivalents for synthesis. Reactions are achieved at rt without the requirement of specialized precautions that are commonplace for other organometallics.
Catalytic asymmetric synthesis of 8-oxabicyclooctanes by intermolecular [5+2] pyrylium cycloadditions
Witten, Michael R.,Jacobsen, Eric N.
supporting information, p. 5912 - 5916 (2014/06/10)
Highly enantioselective intermolecular [5+2] cycloadditions of pyrylium ion intermediates with electron-rich alkenes are promoted by a dual catalyst system composed of an achiral thiourea and a chiral primary aminothiourea. The observed enantioselectivity is highly dependent on the substitution pattern of the 5π component, and the basis for this effect is analyzed using experimental and computational evidence. The resultant 8-oxabicyclo[3.2.1]octane derivatives possess a scaffold common in natural products and medicinally active compounds and are also versatile chiral building blocks for further manipulations. Several stereoselective complexity-generating transformations of the 8-oxabicyclooctane products are presented. A dual thiourea catalyst system enables the title reaction to be carried out to form useful chiral building blocks that can participate in a series of complexity-generating transformations to achieve varied molecular architectures.
Novel γ-secretase inhibitors discovered by library screening of in-house synthetic natural product intermediates
Takahashi, Yasuko,Fuwa, Haruhiko,Kaneko, Akane,Sasaki, Makoto,Yokoshima, Satoshi,Koizumi, Hifumi,Takebe, Tohru,Kan, Toshiyuki,Iwatsubo, Takeshi,Tomita, Taisuke,Natsugari, Hideaki,Fukuyama, Tohru
, p. 3813 - 3816 (2007/10/03)
Screening of our in-house compound library comprised of intermediates of natural product synthesis projects resulted in discovering two novel γ-secretase inhibitors, which coincidently had similar moieties, that is, cyclohexenone and two aryl groups arran
Cadmium-mediated carbonyl benzylation in tap water
Zhou, Cunliu,Wang, Zhiyong
, p. 1649 - 1655 (2007/10/03)
Zn/CdCl2 has been developed as a mediator in the benzylation of various aldehydes in tap water affording the corresponding alcohols in moderate to good yields. The addition of a catalytic amount of InCl3 increases the yield of benzylation product significantly. It can selectively mediate the benzylation of aldehydes in the presence of ketones. A mechanism involving the formation of a cation π-complex is proposed based on the experimental facts. Georg Thieme Verlag Stuttgart.
Silver catalyzed zinc Barbier reaction of benzylic halides in water
Bieber, Lothar W.,Storch, Elisabeth C.,Malvestiti, Ivani,Da Silva, Margarete F.
, p. 9393 - 9396 (2007/10/03)
Benzylic chlorides react in aqueous dibasic potassium phosphate under silver catalysis with aromatic aldehydes in the presence of zinc dust to give 1,2-diaryl alcohols in moderate to good yields. Dimerization to bibenzyls and reduction of the halide are important side reactions. A wide range of substituted aromatic and heteroaromatic aldehydes and of substituted benzylic chlorides can be used. Aliphatic aldehydes and ketones are unreactive. A mechanism of two SET on the metal surface is discussed.
Pseudocine Substitution of 4-(Mesyloxy)-2-cyclopentenones: An Efficient Route to 2,4-Disubstituted 2-Cyclopentenones
West, F. G.,Gunawardena, Gamini
, p. 2402 - 2406 (2007/10/02)
Readily available mesylates 1a-d were found to undergo a novel substitution reaction.In the presence of a variety of nucleophiles, 1a-d underwent a net substitution in which the nucleophile was introduced vicinally (C-3) to the departing mesylate (C-4) and the double bond migrated to C-4/C-5.Lithium bromide, thiophenol, benzylamine, sodium azide, and the potassium salt of dimethyl malonate all led to substitution products in good yield.The reaction is thought to proceed by way of initial conjugate addition of the nucleophile, followed by enolate equilibration and β-elimination of mesylate.
