60550-54-1Relevant academic research and scientific papers
Br?nsted Base-Catalyzed Transformation of α,β-Epoxyketones Utilizing [1,2]-Phospha-Brook Rearrangement for the Synthesis of Allylic Alcohols Having a Tetrasubstituted Alkene Moiety
Kondoh, Azusa,Tasato, Naoko,Aoki, Takuma,Terada, Masahiro
supporting information, p. 5170 - 5175 (2020/07/04)
A stereoselective transformation of α,β-epoxyketones into alkenylphosphates having a hydroxymethyl group on the β-carbon was established by utilizing the [1,2]-phospha-Brook rearrangement under Br?nsted base catalysis. The reaction involves the catalytic generation of an α-oxygenated carbanion located at the α-position of an epoxide moiety through the [1,2]-phospha-Brook rearrangement and the following epoxide opening. Further transformation of the alkenylphosphates by the palladium-catalyzed cross-coupling reaction with Grignard reagents provided allylic alcohols having a stereodefined all-carbon tetrasubstituted alkene moiety.
Transition-Metal-Free Homologative Cross-Coupling of Aldehydes and Ketones with Geminal Bis(boron) Compounds
Stephens, Thomas C.,Pattison, Graham
supporting information, p. 3498 - 3501 (2017/07/15)
We report a transition-metal-free coupling of aldehydes and ketones with geminal bis(boron) building blocks which provides the coupled, homologated carbonyl compound upon oxidation. This reaction not only extends an alkyl chain containing a carbonyl group, it also simultaneously introduces a new carbonyl substituent. We demonstrate that enantiopure aldehydes with an enolizable stereogenic center undergo this reaction with complete retention of stereochemistry.
Expedient Access to 2,3-Dihydropyridines from Unsaturated Oximes by Rh(III)-Catalyzed C-H Activation
Romanov-Michailidis, Fedor,Sedillo, Kassandra F.,Neely, Jamie M.,Rovis, Tomislav
supporting information, p. 8892 - 8895 (2015/08/03)
α,β-Unsaturated oxime pivalates are proposed to undergo reversible C(sp2)-H insertion with cationic Rh(III) complexes to furnish five-membered metallacycles. In the presence of 1,1-disubstituted olefins, these species participate in irreversible migratory insertion to give, after reductive elimination, 2,3-dihydropyridine products in good yields. Catalytic hydrogenation can then be used to convert these molecules into piperidines, which are important structural components of numerous pharmaceuticals.
Oxazaborolidine-catalyzed enantioselective reduction of α-methylene ketones to allylic alcohols
Matsuo, Jun-Ichi,Kozai, Takaaki,Nishikawa, Osamu,Hattori, Yu,Ishibashi, Hiroyuki
, p. 6902 - 6904 (2008/12/22)
(Chemical Equation Presented) Oxazaborolidine-catalyzed enantioselective reduction of α-methylene ketones was efficiently carried out by using borane-diethylaniline as a stoichiometric reducing agent. The combination of this method and subsequent hydrogen
New metal-free one-pot synthesis of substituted allenes from enones
Tang, Meng,Fan, Chun-An,Zhang, Fu-Min,Tu, Yong-Qiang,Zhang, Wen-Xue,Wang, Ai-Xia
supporting information; experimental part, p. 5585 - 5588 (2009/06/18)
(Chemical Equation Presented) A new metal-free, one-pot synthesis of substituted allenes from enones was discovered for the first time, in which a tertiary amine as a base was found to be an effective promoter in such novel transformations. The present synthetic protocol proceeded readily with high compatibility of sensitive functional groups, and it provides a new efficient way to access a series of synthetically important allenes without the use of metallic reagents or catalysts.
Development of an anomalous heck reaction: Skeletal rearrangement of divinyl and enyne carbinols
Ndungu, J. Maina,Larson, Kimberly K.,Sarpong, Richmond
, p. 5845 - 5848 (2007/10/03)
(Chemical Equation Presented) A general set of conditions that achieves the union of aryl halides and divinyl or enyne carbinols to afford tri- or tetrasubstituted olefins in good yields (up to 83%) is described. The mechanism by which this proceeds is believed to involve the intermediacy of a cyclopropanol, followed by a novel skeletal reorganization. The ability to suppress β-hydride elimination of organopalladium intermediates appears to be critical to the success of these processes.
Pd-catalyzed ring opening of cyclopropanols
Okumoto, Hiroshi,Jinnai, Takamitsu,Shimizu, Hiroyuki,Harada, Yoshinori,Mishima, Hideki,Suzuki, Akira
, p. 629 - 630 (2007/10/03)
Treatment of substituted cyclopropanols with a Pd catalyst in MeCN at 50 °C gave enones in good yields.
A Synthesis of an Alkylated Taxane Model System
Bonnert, Roger V.,Jenkins, Paul R.
, p. 413 - 418 (2007/10/02)
A new synthesis of the model compound 8,12,15,15-tetramethyltricyclo3,8>pentadecane using LiCMe2SePh in a method to produce highly substituted dienes is reported.
A New Synthesis of Substituted Dienes and its Application to an Alkylated Taxane Model System
Bonnert, Roger V.,Jenkins, Paul R.
, p. 1540 - 1541 (2007/10/02)
A new synthesis of highly substituted dienes using LiCMe2SePh is reported, along with its application to the synthesis of the taxane model compound 8,12,15,15-tetramethyltricyclo3,8>pentadecane
