- Cu/Pd-catalyzed borocarbonylative trifunctionalization of alkynes and allenes: synthesis of β-geminal-diboryl ketones
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Functionalized bisboryl compounds have recently emerged as a new class of synthetically useful building blocks in organic synthesis. Herein, we report an efficient strategy to synthesize β-geminal-diboryl ketones enabled by a Cu/Pd-catalyzed borocarbonylative trifunctionalization of readily available alkynes and allenes. This reaction promises to be a useful method for the synthesis of functionalized β-geminal-diboryl ketones with broad functional group tolerance. Mechanistic studies suggest that the reaction proceeds through borocarbonylation/hydroboration cascade of both alkynes and allenes. [Figure not available: see fulltext.]
- Yuan, Yang,Wu, Fu-Peng,Spannenberg, Anke,Wu, Xiao-Feng
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p. 2142 - 2153
(2021/09/06)
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- Catalytic Conjunctive Coupling of Carboxylic Acid Derivatives with 9-BBN-Derived Ate Complexes
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β-Boryl carbonyl compounds are produced by a Ni-catalyzed cross-coupling of vinylboron “ate” complexes and acid chloride or acid anhydride electrophiles. The reactions are efficient, being complete in as little as two minutes, and can be applied to a broad range of substrates.
- Law, Chunyin,Meng, Yan,Koo, Seung Moh,Morken, James P.
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supporting information
p. 6654 - 6658
(2019/04/13)
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- FeCl3·6H2O-catalyzed mukaiyama-aldol type reactions of enolizable aldehydes and acetals
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Mukaiyama-aldol type reactions of acetals derived from enolizable aldehydes with FeCl3·6H2O, an eco-friendly, low-cost, and stable catalyst, lead to β-methoxycarbonyl compounds with nearly quantitative yields. The methodology is extended to the parent aldehydes as starting materials, leading to the corresponding aldols with lower yields, but efficiently. Different alkyl and aryl substituted acetals and aldehydes have been tested in the reaction with linear and cyclic silyl enol ethers. Reactions are carried out in an open air atmosphere, and additives are not required. Acetals can be considered activating groups of the carbonyl moiety rather than a protecting group in this type of FeCl3·6H2O-catalyzed condensation.
- Rodríguez-Gimeno, Alejandra,Cuenca, Ana B.,Gil-Tomás, Jesús,Medio-Simón, Mercedes,Olmos, Andrea,Asensio, Gregorio
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p. 8263 - 8270
(2015/03/18)
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- Synthesis of silaoxazolinium salts bearing weakly coordinating anions: Structures and catalytic activities in the aldol reaction
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The synthesis and structures of silaoxazolinium salts 2 and their application to the catalytic Mukaiyama aldol reaction are described. The reaction of (N-amidomethyl)dimethylchlorosilane (1a) or (N-amidomethyl) bis(trimethylsilyl)chlorosilane (1b) with me
- Chandra Sheker Reddy, Anugu,Chen, Zhang,Hatanaka, Tohru,Minami, Tatsuya,Hatanaka, Yasuo
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p. 3575 - 3582
(2013/07/26)
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- Development of N,N-bis(perfluoroalkanesulfonyl)squaramides as new strong Br?nsted acids and their application to organic reactions
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New strong Br?nsted acids derived from a squaric acid scaffold bearing different perfluoroalkanesulfonyl groups have been developed and applied to several organic reactions. These squaramides are bench-stable and exhibit much higher reactivities in several organic reactions than squaric acid itself. N,N-Bis(trifluoromethanesulfonyl)squaramide 2a was applied to the Mukaiyama aldol reaction and Mukaiyama Michael reaction. Mechanistic studies revealed that the Br?nsted acid might be the predominant catalyst through direct protonation of carbonyl compound by the acid itself rather than the silylated Br?nsted acid. The utility of this acid 2a was further extended to Hosomi-Sakurai allylation of aldehydes and a carbonyl-ene reaction. Furthermore, other squaramides 2b and c bearing longer perfluoroalkyl chains have been developed, which are also bench-stable and displayed similar reactivities with squaramide 2a in several organic reactions.
- Cheon, Cheol Hong,Yamamoto, Hisashi
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supporting information; experimental part
p. 4257 - 4264
(2010/07/06)
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- Synthesis and structure of an extremely air-stable binuclear hafnocene perfluorooctanesulfonate complex and its use in lewis acid-catalyzed reactions
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An extremely air-stable μ2-hydroxy-bridged binuclear hafonocene perfluorooctanesulfoante complex was successfully synthesized. This complex showed high catalytic efficiency in the esterification of alcohols, phenol, thiol, and amines, in the Friedel-Crafts acylation of alylaryl ethers, in the Mukaiyama aldol reaction, and in the allylation of aldehydes and could be reused.
- Qiu, Renhua,Zhang, Guoping,Zhu, Yuyang,Xu, Xinhua,Shao, Lingling,Li, Yinhui,An, Delie,Yin, Shuangfeng
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supporting information; scheme or table
p. 6488 - 6494
(2010/02/28)
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- NOVEL BETA-HYDROXYKETONES AND BETA-ALKOXYKETONES WITH ESTROGENIC ACTIVITY
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This invention relates to β-hydroxyketones and β-alkoxyketones of formula (I), to their use as estrogen receptor modulators, and to methods for their preparation.
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Page/Page column 34
(2009/06/27)
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- Synthesis and evaluation of estrogen agonism of diaryl 4,5- dihydroisoxazoles, 3-hydroxyketones, 3-methoxyketones, and 1,3-diketones: A compound set forming a 4D molecular library
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In this paper, the preparation and systematic evaluation of estrogen receptor α (ERα) and estrogen receptor β (ERβ) activities of some diaryl-1,3-diones and their synthetic intermediates, diaryl-4,5-dihydroisoxazoles, diaryl-3-hydroxyketones, diaryl-3-met
- Pulkkinen, Juha T.,Honkakoski, Paavo,Per?kyl?, Mikael,Berczi, Istvan,Laatikainen, Reino
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supporting information; experimental part
p. 3562 - 3571
(2009/04/06)
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- N-heterocyclic carbene-catalyzed Mukaiyama aldol reactions
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(Chemical Equation Presented) N-Heterocyclic carbenes were shown to be highly effective catalysts to promote Mukaiyama aldol reactions. In the presence of only 0.5 mol % of N-heterocyclic carbene (5), various aldehydes and 2,2,2-trifluoroacetophenone unde
- Song, Jinhua J.,Tan, Zhulin,Reeves, Jonathan T.,Yee, Nathan K.,Senanayake, Chris H.
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p. 1013 - 1016
(2007/10/03)
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- Acetate aldol reactions of chiral oxocarbenium ions
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Chiral oxocarbenium ions have been exploited to carry out highly diastereoselective and enantioselective acetate aldol addition reactions. The chiral auxiliary has been optimized to give the product with good diastereoselectivity.
- Kanwar, Sandeep,Trehan, Sanjay
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p. 1329 - 1332
(2007/10/03)
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- Reactive barium-promoted Reformatsky-type reaction of α- chloroketones with aldehydes
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A Reformatsky-type aldol reaction of α-chloroketones with aldehydes has been achieved using reactive barium as a low-valent metal in THF; this one-pot process is more effective for obtaining the desired β-hydroxy ketones in high yields than the stepwise process in which barium enolates are prepared prior to the reaction with aldehydes.
- Yanagisawa, Akira,Takahashi, Hiroshi,Arai, Takayoshi
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p. 580 - 581
(2007/10/03)
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- Decarboxylative aldol reactions of allyl β-keto Esters via heterobimetallic catalysis
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Mild and selective heterobimetallic-catalyzed decarboxylative aldol reactions involving allyl β-keto esters have been developed. The reaction is promoted by Pd(0)- and Yb(III)-DIOP complexes at room temperature and involves the in situ formation of a ketone enolate from allyl β-keto esters followed by addition of the enolate to aldehydes. The reaction is a new example of heterobimetallic catalysis in which the optimized reaction conditions require the addition of both metals. Copyright
- Lou, Sha,Westbrook, John A.,Schaus, Scott E.
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p. 11440 - 11441
(2007/10/03)
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- Stereoselective crossed aldol reaction via boron enolates generated from α-iodo ketones and 9-borabicyclo[3.3.1]nonane
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Boron enolates were in situ-generated reductively by treating various α-iodo ketones such as 2-iodo-1-phenylpropan-1-one, 2-iodo-1-(4-methoxyphenyl)propan-1-one, 2-iodopentan-3-one, 2-iodo-2-methyl-1-phenylpropan-1-one, 3,4-dihydro-2-iodo-1(2H)-naphthalenone, 2-iodo-1-phenylethan-1-one and 1-iodo-4-phenylbutan-2-one with 9-borabicyclo[3.3.1]nonane (9-BBN). Aldols were produced in good yields with good to high diastereoselectivities by subsequent reaction of boron enolates thus formed with various aldehydes. Several boron enolates derived from α-iodo ketones and pinacolatoborane were successfully isolated by distillation, though the yields were rather moderate.
- Mukaiyama, Teruaki,Takuwa, Tomofumi,Yamane, Keiko,Imachi, Shouhei
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p. 813 - 823
(2007/10/03)
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- Reformatsky-type reaction of α-haloketones promoted by titanium tetraiodide
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Titanium(IV) tetraiodide induces a Reformatsky-type reaction of α-iodoketones with carbonyl compounds to give β-hydroxy ketones in good to high yields.
- Shimizu, Makoto,Kobayashi, Fumiko,Hayakawa, Ryuuichirou
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p. 9591 - 9595
(2007/10/03)
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- Diastereoselective aldol and reformatsky reactions of α-halo carbonyl compounds and aldehydes mediated by Titanium(II) Chloride
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Highly diastereoselective aldol reactions of α-bromo ketones with several aldehydes were successfully carried out by using a combination of titanium(II) chloride and copper or sodium iodide in dichloromethane-pivalonitrile at low temperature. Similarly, Reformatsky reactions of α-bromo thioester with aliphatic aldehydes proceeded to afford β-hydroxy thioesters in good yields under mild conditions.
- Kagayama,Igarashi,Shiina,Mukaiyama
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p. 2579 - 2585
(2007/10/03)
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- Uncatalyzed aldol reaction using a dimethylsilyl enolate and α- dimethylsilyl ester in N,N-dimethylformamide
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Dimethylsilyl enolates and α-dimethylsilyl esters reacted with aldehydes in N,N-dimethyl-formamide without an activator to give aldol adducts in moderate to good yields. Under the same conditions, the corresponding trimethylsilyl derivatives exhibited lower reactivities toward the aldol reaction.
- Miura, Katsukiyo,Sato, Hiroshi,Tamaki, Kentaro,Ito, Hajime,Hosomi, Akira
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p. 2585 - 2588
(2007/10/03)
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- Tris(pentafluorophenyl)boron as an Efficient, Air Stable, and Water Tolerant Lewis Acid Catalyst
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Tris(pentafluorophenyl)boron is an efficient, air stable, and water tolerant Lewis acid catalyst for the aldol-type and Michael reactions of silyl enol ethers with carbonyl compounds or other electrophiles (trimethyl orthoformate, dimethal acetal, and chloromethyl methyl ether), the allylation reaction of allylsilanes with aldehydes, and the Diels-Alder reaction of dienes with α,β-unsaturated-aldehydes.A solution of formaldehyde in water is applicable as an electrophile.Also, the aldol-type reaction of ketene silyl acetals with aromatic or aliphatic imines is successfully carried out using the same catalyst.
- Ishihara, Kazuaki,Hanaki, Naoyuki,Funahashi, Miyuki,Miyata, Mayumi,Yamamoto, Hisashi
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p. 1721 - 1730
(2007/10/02)
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- Combined Use of Diphenyltin Sulfide or Lawesson's Reagent and Silver Perchlorate as Effective Catalyst Systems in Aldol Reaction
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Catalytic aldol reactions of several aldehydes with trimethylsilyl enol ethers are effectively performed by combined use of diphenyltin sulfide (Ph2Sn=S) and silver perchlorate (AgClO4) or Lawesson's reagent (2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphos
- Mukaiyama, Teruaki,Saito, Katsuyuki,Kitagawa, Hideo,Shimomura, Naoyuki
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p. 789 - 792
(2007/10/02)
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- Lanthanide trifluoromethanesulfonates as reusable catalysts: Aldol reactions in organic solvents
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The aldol reaction of silyl enolates with aldehydes or acetals using a lanthanide trifluoromethanesulfonate as catalyst smoothly proceed in organic solvents to afford the corresponding aldol-type adducts in high yields. The catalyst can be easily recovere
- Kobayashi,Hachiya,Takahori
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p. 371 - 373
(2007/10/02)
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