103253-60-7Relevant articles and documents
Response surface methodology as an optimization strategy for the light-controlled asymmetric hydrogenation of 4-(trimethylsilyl)-3-butyn-2-one by photosynthetic bacteria
Rui-Hu,Xu, Yun-Sheng,Shao, Dong-Xu,Wang, Meng-Liang
, p. 81 - 88 (2013)
Enantiomerically pure (S)-4-(trimethylsilyl)-3-butyn-2-ol {(S)-TMSBL} is a key intermediate for the synthesis of many biologically and structurally interesting compounds and pharmaceuticals. Herein we propose a new light-controlled asymmetric hydrogenation of 4-(trimethylsilyl)-3-butyn-2-one (TMSBO) to enantiopure (S)-TMSBL by photosynthetic bacteria Rhodobacter sphaeroides, which is a newly isolated photosynthetic bacteria strain that has the capacity to capture light energy and to generate NADPH through photosynthetic electron-transfer reactions; no oxygen or other metabolic intermediates were used. Response Surface Methodology (RSM) was used to investigate the effects of substrate concentration, pH, and temperature on the reaction yield. A 33 factorial design was performed to optimize the production of (S)-TMSBL. The optimum conditions were: cell concentration (200 g/L), shaking speed (140 rpm), pH (6.9), substrate concentration (14.4 mmol/L), and temperature (33.6 °C). This optimization strategy led to an increase of the yield from 88.9% to 94.5%.
A Selective Method for Oxygen Deprotection in Bistrimethylsilylated Terminal Alkynols
Bunce, Richard A.,Hertzler, Donald V.
, p. 3451 - 3453 (1986)
A selective method for oxygen deprotection of bistrimethylsilylated ω-alkynols is described using sulfonic acid type exchange resins in ether solvent.The method offers the advantages of selectivity toward the silicon-oxygen bond, easier monitoring of the reaction and workup, and higher yields (>75percent).Comparisons are made between standart aqueous acid procedures and a series of resins.
A practical synthesis of chiral propargylic alcohols
Ku, Yi-Yin
, p. 2733 - 2736 (1995)
A practical and efficient synthesis of chiral propargylic alcohols has been developed starting from inexpensive and readily available chiral methyl lactate. In addition, a regioselective desilylation method was discovered for oxygen deprotection of bis-silylated alkynols having a terminal trimethylsilyl group.
Selective synthesis of epolactaene featuring efficient construction of methyl (Z)-2-iodo-2-butenoate and (2R,3S,4S)-2-trimethylsilyl-2,3-epoxy-4- methyl-γ-butyrolactone
Tan, Ze,Negishi, Ei-Ichi
, p. 2783 - 2785 (2006)
(+)-Epolactaene was synthesized in 14 steps in the longest linear sequence. The synthesis is highlighted by a highly efficient preparation of the lactone intermediate 4, which only requires three steps from the commercially available (S)-3-butyn-2-ol. It also features a fully stereocontrolled synthesis of the intermediate 9, which was constructed through the use of Zr-catalyzed methylalumination of alkynes and a series of Pd-catalyzed organozinc cross-coupling reactions, such as homopropargylation, direct ethynylation, and alkenylation of the methyl ester of (Z)-α-iodocrotonic acid (3).
Total synthesis of FR901464. Convergent assembly of chiral components prepared by asymmetric catalysis [17]
Thompson,Jamison,Jacobsen
, p. 10482 - 10483 (2000)
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Synthesis of stereopentad analogues of the C14-C22 segment of callystatin A through additions of chiral allenylzinc reagents to stereotriads
Marshall,Schaaf
, p. 7825 - 7831 (2001)
The addition of (P)- and (M)-allenylzinc reagents, prepared in situ through Pd-catalyzed metalation of(R)- and (S)-3-butyn-2-ol mesylates, to diastereomeric stereotriad aldehydes 8, 13, 18, and 23 of syn,syn, syn,anti, anti,anti, and anti,syn stereochemis
Towards the Total Synthesis of Jerangolids – Synthesis of an Advanced Intermediate for the Pharmacophore Substructure
Huch, Volker,Hutter, Michael,Jauch, Johann,Lenhof, Julian
, p. 5833 - 5840 (2020)
The jerangolids are a class of natural products with a skipped diene substructure isolated from Sorangium cellulosum. Here, we present a new strategy for the total synthesis of these compounds based on a skipped diyne as central building block and a suitably substituted epoxy aldehyde as building block for the dihydropyran substructure. So far, we reached an advanced intermediate which is related to the pharmacophore subunit of the jerangolids as well as of the ambruticins. A key step is a Shi epoxidation with high e.r. to form the epoxy aldehyde. Both building blocks are coupled in a Carreira alkynylation, where additional mechanistic studies based on DFT calculation were realized. The alkynylation is followed by a nucleophilic 6-endo-tet epoxide opening to form the pyran structure and a Nicholas reduction to remove a propargylic OH group.
A boron-oxygen transborylation strategy for a catalytic midland reduction
Nicholson, Kieran,Dunne, Joanne,DaBell, Peter,Garcia, Alexander Beaton,Bage, Andrew D.,Docherty, Jamie H.,Hunt, Thomas A.,Langer, Thomas,Thomas, Stephen P.
, p. 2034 - 2040 (2021/02/20)
The enantioselective hydroboration of ketones is a textbook reaction requiring stoichiometric amounts of an enantioenriched borane, with the Midland reduction being a seminal example. Here, a turnover strategy for asymmetric catalysis, boron.oxygen transb
Asymmetric Magnesium-Catalyzed Hydroboration by Metal-Ligand Cooperative Catalysis
Falconnet, Alban,Magre, Marc,Maity, Bholanath,Cavallo, Luigi,Rueping, Magnus
supporting information, p. 17567 - 17571 (2019/11/13)
Asymmetric catalysis with readily available, cheap, and non-toxic alkaline earth metal catalysts represents a sustainable alternative to conventional synthesis methodologies. In this context, we describe the development of a first MgII-catalyzed enantioselective hydroboration providing the products with excellent yields and enantioselectivities. NMR spectroscopy studies and DFT calculations provide insights into the reaction mechanism and the origin of the enantioselectivity which can be explained by a metal-ligand cooperative catalysis pathway involving a non-innocent ligand.
