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91.
Atsuhiro Iimuro Kosuke Higashida Yusuke Kita Kazushi Mashima 《Advanced Synthesis \u0026amp; Catalysis》2016,358(12):1929-1933
We describe a most straightforward synthetic method for preparing neurokinin‐1 (NK1) receptor antagonist derivatives by asymmetric hydrogenation of 3‐amido‐2‐arylpyridinium salts using dinuclear iridium complexes with enantiopure diphosphine ligands, affording the corresponding chiral piperidines in high cis‐diastereoselectivity (>95:5) and moderately high enantioselectivity (up to 86%). Deprotection treatments afforded the NK‐1 receptor antagonist (+)‐CP‐99,994 (83% ee). In addition, we observed unique additive effects of 10‐camphorsulfonic acid in the asymmetric hydrogenation of 3‐amido‐2‐arylpyridinium salts.
92.
Danila Gasperini Lorenzo Maggi Stphanie Dupuy Richard M. P. Veenboer David B. Cordes Alexandra M. Z. Slawin Steven P. Nolan 《Advanced Synthesis \u0026amp; Catalysis》2016,358(23):3857-3862
The improved synthesis of γ‐, δ‐ and ϵ‐lactones using a dinuclear N‐heterocyclic carbene (NHC)‐gold(I) catalyst is reported. This solvent‐free process provides access to γ‐ and δ‐lactones in high regio‐ and stereoselectivity. Reactions were performed at low catalyst loadings and without the need for any additives. The use of a digold pre‐catalyst provides a new synthetic route to functionalised ϵ‐lactones, poorly accessible using previous methodologies.
93.
Marc Renom‐Carrasco Piotr Gajewski Luca Pignataro Johannes G. deVries Umberto Piarulli Cesare Gennari Laurent Lefort 《Advanced Synthesis \u0026amp; Catalysis》2016,358(16):2589-2593
Herein we describe a new methodology for the asymmetric hydrogenation (AH) of 2‐substituted pyridinium salts. An iridium catalyst based on a mixture of a chiral monodentate phosphoramidite and an achiral phosphine was shown to hydrogenate N‐benzyl‐2‐arylpyiridinium bromides to the corresponding N‐benzyl‐2‐arylpiperidines with full conversion and good enantioselectivity. The mechanism of the reaction under optimized conditions was investigated via kinetic measurements and isotopic labeling experiments. Our study suggests that the hydrogenation starts with a 1,4‐hydride addition and that the enantiodiscriminating step involves the reduction of an iminium intermediate.
94.
Ruwei Shen Jianlin Yang Bing Luo Lixiong Zhang Li‐Biao Han 《Advanced Synthesis \u0026amp; Catalysis》2016,358(23):3897-3906
The copper‐catalyzed reaction of 5‐substituted penta‐1,4‐diyn‐3‐yl acetates with P(O)H compounds to efficiently give a new class of phosphonyl diynes is reported. The reaction may take place through a regioselective nucleophilic attack of phosphorus nucleophiles on Cu‐allenylidene intermediates to form allenyl intermediates followed by a rapid allene‐alkyne isomerization process. The synthetic utility of the obtained products is demonstrated.
95.
Jun Wu Yanjun Xie Xiangui Chen Guo‐Jun Deng 《Advanced Synthesis \u0026amp; Catalysis》2016,358(20):3206-3211
An efficient strategy for carbazole synthesis from arylureas and cyclohexanones under transition metal‐free conditions has been developed. The combined use of potassium iodide and iodine could significantly improve the reaction efficiency to provide 2,6‐disubstituted 9‐arylcarbazoles in moderate to good yields. In this kind of transformation, the whole carbazole moiety (except the nitrogen atom) comes from two equivalents of cyclohexanones.
96.
Svetlana Tupova Matthias Rudolph Frank Rominger A. Stephen K. Hashmi 《Advanced Synthesis \u0026amp; Catalysis》2016,358(24):3999-4005
The nucleophilic addition of protected and substituted hydrazine derivatives to isonitrile complexes of gold(I), platinum(II), palladium(II) and rhodium(III) provides the corresponding hydrazino amino acyclic carbene complexes. These are characterized by their spectroscopic data, four different X‐ray single crystal structure analyses and their catalytic activity in the gold(I)‐catalyzed cycloisomerization of N‐propargylcarboxamides to alkylideneoxazolines is investigated.
97.
Yang Wu Yang Liu Wenjun Yang Honglei Liu Leijie Zhou Zhanhu Sun Hongchao Guo 《Advanced Synthesis \u0026amp; Catalysis》2016,358(22):3517-3521
With the use of a bifunctional chiral phosphine as the catalyst, the asymmetric [3+2] annulation of Morita–Baylis–Hillman carbonates with cyclic 1‐azadienes proceeded smoothly under mild conditions to give various enantiomerically enriched cyclopentene derivatives bearing three consecutive tertiary stereocenters and a sulfamate moiety in moderate to excellent yields with moderate to excellent enantioselectivities and excellent diastereoselectivities.
98.
Bruno R. S. Paula Davila Zampieri J. Augusto R. Rodrigues Paulo J. S. Moran 《Advanced Synthesis \u0026amp; Catalysis》2016,358(22):3555-3571
(Z)‐3‐Acetoxymethyl‐4‐R‐3‐buten‐2‐ones (R=aryl, alkyl) and (Z)‐3‐methyl‐4‐R‐3‐buten‐2‐ones (R=aryl) were synthesized and submitted to reduction by the yeast Saccharomyces cerevisiae producing the (R)‐ and (S)‐4‐R‐3‐methybutan‐2‐ones, respectively. This stereochemistry control strategy was applied in the syntheses of (R)‐ and (S)‐Tropional® with moderate to high enantiomeric excesses. Other (Z)‐3‐acyloxymethyl‐4‐phenyl‐3‐buten‐2‐ones showed similar behavior to the (Z)‐3‐acetoxymethyl counterpart, and the acylated Morita–Baylis–Hillman adduct 1‐acetoxy‐2‐methylene‐1‐phenylbutan‐3‐one produced a mixture of products, with and without the acetoxy group, via three different reaction pathways. In addition to experiments employing whole cells, those in which isolated enereductases were used suggested that the main pathway through which the loss of the acetoxy group occurs during the biocatalytic cascade is an SN2′‐type reaction, rather than formal hydrogen addition followed by acetic acid elimination. Finally, related ethyl enones were reduced enantioselectively by the yeast Candida albicans, producing both (R)‐ and (S)‐reduction products, depending on the presence of the acetoxy group in the starting material.
99.
Yu‐Rong Chen Gu Zhan Wei Du Ying‐Chun Chen 《Advanced Synthesis \u0026amp; Catalysis》2016,358(23):3759-3764
A highly regio‐, diastereo‐ and enantioselective formal (3+2) cycloaddition reaction of nitrone ylides from isatins and α,β‐unsaturated aldehydes was developed via iminium catalysis in the presence of an additional base, furnishing a spectrum of 1′‐hydroxy‐3,2′‐pyrrolidinylspirooxindole frameworks. Interestingly, the regioselectivity could be finely switched in the reactions between nitrone ylides and crotonaldehyde by adding catalytic amounts of lithium perchlorate and copper(II) bromide.
100.
Liang Wei Zuo‐Fei Wang Lu Yao Guofu Qiu Haiyan Tao Hua Li Chun‐Jiang Wang 《Advanced Synthesis \u0026amp; Catalysis》2016,358(24):3955-3959
An unprecedented copper(II)‐catalyzed enantioselective 1,3‐dipolar [3+4] cycloaddition of azomethine imines with in situ formed azoalkenes has been realized. This strategy provides a facile access to biologically important 1,2,4,5‐tetrazepine derivatives in high yield with exclusive regioselectivity and high stereoselectivity. Moreover, enantioenriched azomethine imines could be obtained via an efficient kinetic resolution using the same approach.