+ Resolve Article
+ Follow Us
Follow on FacebookFollow on Facebook
Follow on TwitterFollow on Twitter

+ Translate
+ Subscribe to Site Feed
GeoScience Most Shared ContentMost Shared Content

Organic chemistry. Rh-catalyzed C-C bond cleavage by transfer hydroformylation

, : Organic chemistry. Rh-catalyzed C-C bond cleavage by transfer hydroformylation. Science 347(6217): 56-60

The dehydroformylation of aldehydes to generate olefins occurs during the biosynthesis of various sterols, including cholesterol in humans. Here, we implement a synthetic version that features the transfer of a formyl group and hydride from an aldehyde substrate to a strained olefin acceptor. A Rhodium (Xantphos)(benzoate) catalyst activates aldehyde carbon-hydrogen (C-H) bonds with high chemoselectivity to trigger carbon-carbon (C-C) bond cleavage and generate olefins at low loadings (0.3 to 2 mole percent) and temperatures (22° to 80°C). This mild protocol can be applied to various natural products and was used to achieve a three-step synthesis of (+)-yohimbenone. A study of the mechanism reveals that the benzoate counterion acts as a proton shuttle to enable transfer hydroformylation.


PMID: 25554782

DOI: 10.1126/science.1261232

Other references

International Atomic Energy Agency, 1962: Geology of uranium and thorium. This volume contains a guide to the literature including almost 200 entries on bibliographies, periodicals, reports and proceedings of conferences, arranged by countries. There are 8 chapters, viz.: Geology of Radioactive Occurrences, (189 referen...

Boliakina, G.K., 1979: Myocardial contractile capacity and the central hemodynamic indices in the initial period after resuscitation. Anesteziologiia i Reanimatologiia: 43-46

Bonten, M.J.M., 2015: Colonization pressure: a critical parameter in the epidemiology of antibiotic-resistant bacteria. The recognition of colonization pressure as an important risk factor for acquisition of antibiotic-resistant bacteria in the ICU, including Acinetobacter species, has major consequences for our understanding of risk factor analyses. Moreover, the...

Jones, L.R.; Knopke, H.J., 1987: Educating family physicians to care for the chronically mentally ill. More than 50 percent of the chronically mentally ill receive their medical, psychiatric, and social support services from primary care physicians in the general health sector. Despite this high level of involvement with these patients, the majorit...

Revillard, J.P.; Adorini, L.; Goldman, M.; Kabelitz, D.; Waldmann, H., 1998: Apoptosis: potential for disease therapies. Immunology Today 19(7): 291-293

Turner J.E.; Parry J.M., 1989: The induction and repair of dna damage in the mussel mytilus edulis. Marine Environmental Research 28(1-4): 346-348

Degen, A.V., 1933: Bemerkungen iiber einige orien-talische Pflanzenarten. The following are new: Crepis nestmeieri (p.64), Dianthus pinifolius sspp. hermanni and thracicus (p.65), and Tulipa helles-pontica, all E. Thrace; Pedicularis jriderici-augusti ssp. drenowskii (p.147), Polygala comosa ssp. alibotusense, Alyssum m...

Henninger, C.; Nelson, G., 1984: Evaluation of a social support program for young unwed mothers. This research evaluated the effects of a social support program on young unwed mothers. Measures of social support, stress, affect, and life events were compiled by 15 program participants and 15 matched controls before and after the program six m...

Kapitulnik, J.; Bibi, O.; Koren, R., 1982: Early changes in growth control of cells in culture induced by a chemical carcinogen. The effects of the chemical carcinogen N-methyl-N'-nitro-N-nitrosoguanidine (MNNG) on 'early events' in cellular response to growth stimulation were studied in quiescent (confluent and serum-starved) baby hamster kidney C13 and seco...

Overgaard-Steensen, C.; Ring, T., 2015: Clinical review: practical approach to hyponatraemia and hypernatraemia in critically ill patients. Disturbances in sodium concentration are common in the critically ill patient and associated with increased mortality. The key principle in treatment and prevention is that plasma [Na+] (P-[Na+]) is determined by external water and cation balances...