32556-70-0Relevant articles and documents
Enantioselective cathodic reduction of some prochiral ketones in the presence of (-)-N,N′-dimethylquininium tetrafluoroborate at mercury cathode
Yadav, Ashok K.,Manju, Meera,Chhinpa, Pukh Raj
, p. 1079 - 1081 (2003)
This work describes preparative scale enantioselective cathodic reduction of some prochiral ketones, viz. 3,4-dihydro-1(2H)-naphthaleneone, 2-octanone, 1-phenyl-2-propanone, E-3-octen-2-one, 1-octyn-3-one, 1-undecyn-3-one, 1-tetradecyn-3-one at mercury pool in N,N-dimethyl formamide (DMF)-2-propanol (9.5:0.5), using tetrabutylammonium tetrafluoroborate (TBA·BF4), as supporting electrolyte and (-)-N,N′-dimethylquininium tetrafluoroborate (DMQ·2BF4), as a enantioselective inductor. The products obtained were corresponding (S)-alcohols in 24-70% ee.
Novel chemoenzymatic strategy for the synthesis of enantiomerically pure secondary alcohols with sterically similar substituents
Abad, Jose-Luis,Soldevila, Carles,Camps, Francisco,Clapes, Pere
, p. 5351 - 5356 (2003)
A novel chemoenzymatic strategy for the synthesis of enantiomerically pure secondary alcohols with sterically similar substituents is described. The key step is the kinetic lipase-catalyzed resolution of racemic mixtures of substituted propargylic alcohols. The efficiency of this new approach was tested in the preparation of the corresponding enantiomers of 1,11-hexadecandiol derivatives ((R)-5 and (S)-5). Two strategies were tested. In the first one, the racemic intermediate 1-octyn-3-ol (1) was resolved enzymatically and then elongated with 1-bromo-9,11-dioxadodecane. Alternatively, the racemic 1 can be elongated to the corresponding racemic 17,19-dioxa-7-eicosyn-6-ol (3) first and then resolved biocatalytically. Twelve commercially available lipases were screened for the kinetic resolution of these intermediates. Among them, Candida antarctica lipase (CAL-B) and Humicola lanuginosa lipase (HLL) were the best biocatalysts for the resolution of 1 (S enantiomer 90% ee, E = 35), and 3 (R enantiomer 90% ee, E = 34), respectively.
Palladium-catalyzed propargylic substitution with phosphorus nucleophiles: Efficient, stereoselective synthesis of allenylphosphonates and related compounds
Kalek, Marcin,Johansson, Tommy,Jezowska, Martina,Stawinski, Jacek
, p. 4702 - 4704 (2010)
A new, efficient method is developed, based on a palladium(0)-catalyzed reaction of propargylic derivatives with various phosphorus nucleophiles, to produce allenylphosphonates and their analogues with defined stereochemistry in the allenic and the phosph
Practical preparation of both optically pure enantiomers of but-1-yn-3-ol, oct-1-yn-3-ol and 6-methylhept-2-yn-4-ol using biocartol as resolving agent
Michelet,Besnier,Tanier,Touzin,Genet,Demoute
, p. 165 - 167 (1995)
A new facile preparation of optically pure secondary alkynols has been developed. This involves resolution of the corresponding racemic alcohols using biocartol as the resolving agent.
A Lipase Mediated Asymmetric Hydrolysis of 3-Acyloxy-1-octynes and 3-(E)-Acyloxy-1-octenes
Shimizu, Makoto,Kawanami, Hiroshi,Fujisawa, Tamotsu
, p. 107 - 110 (1992)
Optical resolution of 3-propionyloxy-1-trimethylsilyl-1-octyne or 3-(E)-propionyloxy-1-octene via lipase-mediated hydrolysis gave optically pure (S)-1-trimethylsilyl-1-octyn-3-ol and (R)-(E)-1-iodo-1-octen-3-ol, respectively, in which a reversal of enantio-selectivity for hydrolysis was observed between 3-propionyloxy-1-octyn and its 1-trimethylsilylated derivative, and the effect of the acyl groups on the enantio-discrimination was also investigated.
Optically active propargylic and allylic alcohols with a difluoromethyl group at the terminal carbon
Xiao, Ling,Kitazume, Tomoya
, p. 3597 - 3601 (1997)
Enantioselective esterification of α-substituted propargylic alcohols was found to proceed very smoothly in the presence of a catalytic amount of lipase (Nobozym 435) to yield the corresponding (R)-alcohols and (S)-acetates with high enantiomeric excess. Further, the preparation of optically active propargylic and allylic alcohols with a difluoromethyl group at the terminal carbon is described.
Ester Synthesis in Water: Mycobacterium smegmatis Acyl Transferase for Kinetic Resolutions
de Leeuw, Nicolas,Torrelo, Guzman,Bisterfeld, Carolin,Resch, Verena,Mestrom, Luuk,Straulino, Emanuele,van der Weel, Laura,Hanefeld, Ulf
, p. 242 - 249 (2017/11/16)
The acyl transferase from Mycobacterium smegmatis (MsAcT) catalyses transesterification reactions in aqueous media because of its hydrophobic active site. Aliphatic cyanohydrin and alkyne esters can be synthesised in water with excellent and strikingly opposite enantioselectivity [(R);E>37 and (S);E>100, respectively]. When using this enzyme, the undesired hydrolysis of the acyl donor is an important factor to take into account. Finally, the choice of acyl donor can significantly influence the obtained enantiomeric excesses. (Figure presented.).
Highly Selective Manganese(I)/Lewis Acid Cocatalyzed Direct C?H Propargylation Using Bromoallenes
Zhu, Can,Schwarz, Jonas Luca,Cembellín, Sara,Gre?ies, Steffen,Glorius, Frank
supporting information, p. 437 - 441 (2018/02/21)
A manganese(I)/Lewis acid cocatalyzed direct C?H propargylation with high selectivity has been developed. BPh3 was discovered to not only promote the reactivity, but also enhance the selectivity. Secondary, tertiary, and even quaternary carbon centers at the propargylic position could be directly constructed. Both internal and terminal alkynes are easily accessible. The chirality was successfully transferred from an axially chiral allene to central chirality. The reactivity of the manganese catalyst in this reaction was found to be unique among transition metal catalysts.
Asymmetric Total Syntheses of Two Possible Diastereomers of Gliomasolide e and Its Structural Elucidation
Reddy, Ramidi Gopal,Venkateshwarlu, Ravula,Ramakrishna, Kallaganti V. S.,Yadav, Jhillu S.,Mohapatra, Debendra K.
, p. 1053 - 1063 (2018/06/18)
The first total syntheses of two possible diastereomers of gliomasolide E, a 14-membered macrolides isolated from the marine sponge Phakellia fusca Thiele, which was collected from the South China Sea, is reported. Highlights of the synthesis include macrolactonization through intramolecular Horner-Wadsworth-Emmons olefination, Yamaguchi-Hirao alkynylation, and base-induced elimination reactions for propargyl alcohol synthesis as the key reactions. Detailed comparison of their 1H and 13C NMR (1D and 2D NMR data) and specific rotation with those of the natural product revealed that the absolute stereochemistry of gliomasolide E should be (2E,5R,7R,9R,13R).
A general asymmetric synthesis of (R)-Matsutakeol and flavored analogs
Liu, Jia,Li, Honglian,Zheng, Chao,Lu, Shichao,Guo, Xianru,Yin, Xinming,Na, Risong,Yu, Bin,Wang, Min
, (2017/03/15)
An efficient and practical synthetic route toward chiral matsutakeol and analogs was developed by asymmetric addition of terminal alkyne to aldehydes. (R)-matsutakeol and other flavored substances were feasibly synthesized from various alkylaldehydes in high yield (up to 49.5%, in three steps) and excellent enantiomeric excess (up to >99%). The protocols may serve as an alternative asymmetric synthetic method for active small-molecule library of natural fatty acid metabolites and analogs. These chiral allyl alcohols are prepared for food analysis and screening insect attractants.
