49642-49-1Relevant articles and documents
Enantiopure Acetals of α-Alkynyl Carbonyl Compounds: Organoaluminum-Mediated 1,2-Shift of Cobalt-Complexed Alkynyl Group with Concomitant Capture by a Nucleophile
Taya, Kimiko,Nagasawa, Tetsuya,Suzuki, Keisuke
, p. 304 - 306 (1997)
Upon treatment with the organoaluminum-based combination of Lewis acid and nucleophile, chiral mesyloxy acetal having a Co-complexed alkynyl group undergoes stereospecific 1,2-shift of the complexed alkynyl and the concomitant attack of the ligand R of the organoaluminum reagent. Decomplexation of the products with CAN gives the chiral acetals of α-alkynyl carbonyl compounds in enantiomerically pure form in high yields.
Chemo- And regioselective hydroformylation of alkenes with CO2/H2over a bifunctional catalyst
Hua, Kaimin,Liu, Xiaofang,Wei, Baiyin,Shao, Zilong,Deng, Yuchao,Zhong, Liangshu,Wang, Hui,Sun, Yuhan
supporting information, p. 8040 - 8046 (2021/11/01)
As is well known, CO2 is an attractive renewable C1 resource and H2 is a cheap and clean reductant. Combining CO2 and H2 to prepare building blocks for high-value-added products is an attractive yet challenging topic in green chemistry. A general and selective rhodium-catalyzed hydroformylation of alkenes using CO2/H2 as a syngas surrogate is described here. With this protocol, the desired aldehydes can be obtained in up to 97% yield with 93/7 regioselectivity under mild reaction conditions (25 bar and 80 °C). The key to success is the use of a bifunctional Rh/PTA catalyst (PTA: 1,3,5-triaza-7-phosphaadamantane), which facilitates both CO2 hydrogenation and hydroformylation. Notably, monodentate PTA exhibited better activity and regioselectivity than common bidentate ligands, which might be ascribed to its built-in basic site and tris-chelated mode. Mechanistic studies indicate that the transformation proceeds through cascade steps, involving free HCOOH production through CO2 hydrogenation, fast release of CO, and rhodium-catalyzed conventional hydroformylation. Moreover, the unconventional hydroformylation pathway, in which HCOOAc acts as a direct C1 source, has also been proved to be feasible with superior regioselectivity to that of the CO pathway.
ALDEHYDE GENERATION VIA ALKENE HYDROFORMYLATION
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Paragraph 0035; 0079-0081, (2021/09/26)
Aldehyde generation includes providing a first input stream, a second input, and an alkene substrate to a reactor system. The first input stream includes a catalyst, a ligand, and an organic solvent. The second input stream includes a mixture of carbon monoxide (CO) and hydrogen gas (H2). The alkene substrate is in either gaseous form or liquid form, the liquid form of the alkene substrate being provided with the first input stream, the gaseous form of the alkene substrate being provided with the second input stream. The reactor system includes a first reactor and a second reactor, where the second reactor is gas permeable and positioned within the first reactor.