- A One-Pot Approach to 2-Substituted-2-(Dimethoxyphosphoryl)-Pyrrolidines from Substituted tert-Butyl 4-Oxobutylcarbamates and Trimethyl Phosphite
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A novel approach to 2-substituted-2-(dimethoxyphosphoryl)-pyrrolidines 7a-7o and 9a-9r has been developed, which features a TMSOTf-mediated one-pot intramolecular cyclization and phosphonylation of substituted tert-butyl 4-oxobutylcarbamates. The major advantages of this method include simple operation under mild reaction conditions, the use of cheap Lewis acid, and good to excellent yields with high diastereoselectivities (dr up to 99:1).
- Chen, Zhao-Dan,Xu, Wen-Ke,Guo, Jia-Ming,Chen, Ling,Wei, Bang-Guo,Si, Chang-Mei,Lin, Guo-Qiang
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- Iron-Catalysed Remote C(sp3)?H Azidation of O-Acyl Oximes and N-Acyloxy Imidates Enabled by 1,5-Hydrogen Atom Transfer of Iminyl and Imidate Radicals: Synthesis of γ-Azido Ketones and β-Azido Alcohols
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In the presence of a catalytic amount of iron(III) acetylacetonate [Fe(acac)3], the reaction of structurally diverse ketoxime esters with trimethylsilyl azide (TMSN3) afforded γ-azido ketones in good to excellent yields. This unprecedented distal γ-C(sp3)?H bond azidation reaction went through a sequence of reductive generation of an iminyl radical, 1,5-hydrogen atom transfer (1,5-HAT) and iron-mediated redox azido transfer to the translocated carbon radical. TMSN3 served not only as a nitrogen source to functionalise the unactivated C(sp3)?H bond, but also as a reductant to generate the catalytically active FeII species in situ. Based on the same principle, a novel β-C(sp3)?H functionalisation of alcohols via N-acyloxy imidates was subsequently realised, leading, after hydrolysis of the resulting ester, to β-azido alcohols, which are important building blocks in organic and medicinal chemistry.
- Torres-Ochoa, Rubén O.,Leclair, Alexandre,Wang, Qian,Zhu, Jieping
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supporting information
p. 9477 - 9484
(2019/05/21)
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- Enantioselective Synthesis of 2-Substituted Pyrrolidines via Intramolecular Reductive Amination
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Catalyzed by the complex generated in situ from iridium and the chiral ferrocene ligand, tert -butyl (4-oxo-4-arylbutyl)carbamate substrates were deprotected and then reductively cyclised to form 2-substituted arylpyrrolidines in a one-pot manner, in which the intramolecular reductive amination was the key step. A range of chiral 2-substituted arylpyrrolidines were synthesised in up to 98percent yield and 92percent ee.
- Chang, Mingxin,Guo, Haodong,Huang, Haizhou,Zhang, Tao,Zhao, Wenlei,Zhou, Huan
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p. 2713 - 2719
(2019/06/19)
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- Probing the Effects of Heterocyclic Functionality in [(Benzene)Ru(TsDPENR)Cl] Catalysts for Asymmetric Transfer Hydrogenation
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A range of TsDPEN catalysts containing heterocyclic groups on the amine nitrogen atom were prepared and evaluated in the asymmetric transfer hydrogenation of ketones. Bidentate and tridentate ligands demonstrated a mutual exclusivity directly related to their function as catalysts. A broad series of ketones were reduced with these new catalysts, permitting the ready identification of an optimal catalyst for each substrate and revealing the subtle effects that changes to nearby donor groups can exhibit.
- Barrios-Rivera, Jonathan,Xu, Yingjian,Wills, Martin
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supporting information
p. 7223 - 7227
(2019/10/08)
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- Bcl-2 INHIBITORS
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Disclosed herein is a compound of Formula (I) for inhibiting Bcl-2 and treating disease associated with undesirable bcl-2 activity (Bcl-2 related diseases), a method of using the compounds disclosed herein for treating dysregulated apoptotic diseases including cancers and treating autoimmune disease, and a pharmaceutical composition comprising the same.
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Paragraph 0239; 0240; 0241
(2019/11/19)
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- Enantioselective Direct Synthesis of Free Cyclic Amines via Intramolecular Reductive Amination
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Chiral cyclic amines can be prepared via intramolecular reductive amination of N-Boc-protected amino ketones in a one-pot process. With the complex of iridium and f-spiroPhos as the catalyst, a range of N-Boc-protected amino ketones are smoothly transformed into chiral cyclic free amines in high yields and excellent enantioselectivities (up to 97% ee). Moreover, this method can also be successfully applied to the synthesis of a κ-opioid receptor selective antagonist, (S)-1.
- Zhang, Ying,Yan, Qiaozhi,Zi, Guofu,Hou, Guohua
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supporting information
p. 4215 - 4218
(2017/08/23)
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- Rhodium(III)-Catalyzed [3+2] Annulation of 5-Aryl-2,3-dihydro-1H-pyrroles with Internal Alkynes through C(sp2)-H/Alkene Functionalization
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This study describes a new rhodium(III)-catalyzed [3+2] annulation of 5-aryl-2,3-dihydro-1H-pyrroles with internal alkynes using a Cu(OAc)2 oxidant for building a spirocyclic ring system, which includes the functionalization of an aryl C(sp2)-H bond and addition/protonolysis of an alkene C=C bond. This method is applicable to a wide range of 5-aryl-2,3-dihydro-1H-pyrroles and internal alkynes, and results in the assembly of the spiro[indene-1,2′-pyrrolidine] architectures in good yields with excellent regioselectivities.
- Zhou, Ming-Bo,Pi, Rui,Hu, Ming,Yang, Yuan,Song, Ren-Jie,Xia, Yuanzhi,Li, Jin-Heng
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supporting information
p. 11338 - 11341
(2016/02/19)
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- On the synthesis of α-amino sulfoxides
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A synthetic study on the preparation of N-Boc α-amino sulfoxides has revealed an unexpected instability which is believed to be due to α-elimination of the sulfoxide to give an iminium ion. Full synthetic details are reported on two main synthetic routes: lithiation and sulfinate trapping of N-Boc heterocycles and oxidation of N-Boc α-amino sulfides. Six novel α-amino sulfoxides were successfully prepared and isolated. It is speculated that four other α-amino sulfoxides were synthesised but could not be isolated due to their propensity to α-eliminate the sulfoxide. Ultimately, a stable, cyclic N-Boc α-amino sulfoxide was prepared and this successful synthesis relied on the α-amino sulfoxide being part of a bicyclic [3.1.0] fused ring system that could not undergo α-elimination of the sulfoxide. the Partner Organisations 2014.
- Rayner, Peter J.,Gelardi, Giacomo,O'Brien, Peter,Horan, Richard A. J.,Blakemore, David C.
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p. 3499 - 3512
(2014/05/20)
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- PYRIDO PYRIMIDINES
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Compounds of formula and pharmaceutically acceptable salts thereof are described, as well as the pharmaceutical compositions containing said compounds and their pharmaceutically acceptable salts, and the use of said compounds and pharmaceutical compositions for the treatment, control or amelioration of proliferative diseases, including cancer, Down syndrome or early onset Alzheimer's disease.
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Page/Page column 109
(2012/07/28)
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- Highly effective asymmetric hydrogenation of cyclic N -alkyl imines with chiral cationic Ru-MsDPEN catalysts
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A range of cyclic N-alkyl imines were efficiently hydrogenated by using a chiral cationic Ru(η6-cymene)(MsDPEN)(BArF) complex (MsDPEN = N-(methanesulfonyl)-1,2-diphenylethylenediamine) in high yields and up to 98% ee. A one-pot synthesis of chiral 2-phenylpyrrolidine via reductive amination was also developed.
- Chen, Fei,Ding, Ziyuan,Qin, Jie,Wang, Tianli,He, Yanmei,Fan, Qing-Hua
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supporting information; experimental part
p. 4348 - 4351
(2011/10/13)
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- A chemo-enzymatic route to enantiomerically pure cyclic tertiary amines
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Deracemization of racemic chiral tertiary amines has been achieved by combination of an enantioselective amine oxidase, obtained through directed evolution, and ammonia borane in a one-pot process. Copyright
- Dunsmore, Colin J.,Carr, Reuben,Fleming, Toni,Turner, Nicholas J.
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p. 2224 - 2225
(2007/10/03)
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- MITOTIC KINESIN INHIBITORS AND METHODS OF USE THEREOF
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This invention relates to inhibitors of mitotic kinesins, particularly KSP, and methods for producing these inhibitors. The invention also provides pharmaceutical compositions comprising the inhibitors of the invention and methods of utilizing the inhibitors and pharmaceutical compositions in the treatment and prevention of various disorders.
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Page/Page column 55
(2010/11/08)
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- A One-Pot Process for the Enantioselective Synthesis of Amines via Reductive Amination under Transfer Hydrogenation Conditions
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(Equation presented) Cyclic amines may be prepared via a sequence of deprotection followed by intramolecular reductive amination of t-Boc-protected amino ketones under asymmetric transfer hydrogenation conditions. In cases where the corresponding imine reaction proceeds with high enantioselectivity, this is reflected in the one-step process.
- Williams, Glynn D.,Pike, Richard A.,Wade, Charles E.,Wills, Martin
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p. 4227 - 4230
(2007/10/03)
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- Organometallic Ring-Opening Reactions of N-Acyl and N-Alkoxycarbonyl Lactams. Synthesis of Cyclic Imines
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The reactions of hexyl- and phenylmagnesium bromides with N-acyl and N-alkoxycarbonyl lactams in tetrahydrofuran at -78 deg C have been performed to determine the factors affecting the regioselectivity.N-Pivaloyl γ- and δ-lactams undergo the ring-opening reactions with both Grignard reagents, whereas on the N-benzoyl γ-lactam a complete selectivity is achieved only with phenylmagnesium bromide.The N-Cbz γ- and δ-lactams preferentially react at the exocyclic carbonyl group, especially with hexylmagnesium bromide.The N-Boc five- to eight-membered lactams undergo the ring-opening reaction to give N-Boc-ω-amino ketones, although the efficiency slightly decreases by increasing the ring size.The deprotection of the N-Boc-ω-amino ketones with trifluoroacetic acid easily affords the corresponding five- to seven-membered cyclic imines.Pyridine alkaloids containing the cyclic imine moiety have been prepared by a modified route, exploiting the more easily available pyridyllithium reagents, instead of the corresponding Grignard reagents.
- Giovannini, Arianna,Savoia, Diego,Umani-Ronchi, Achille
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p. 228 - 234
(2007/10/02)
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