54774-82-2Relevant academic research and scientific papers
Triphosgene and DMAP as Mild Reagents for Chemoselective Dehydration of Tertiary Alcohols
Ganiu, Moshood O.,Cleveland, Alexander H.,Paul, Jarrod L.,Kartika, Rendy
supporting information, p. 5611 - 5615 (2019/08/01)
The utility of triphosgene and DMAP as mild reagents for chemoselective dehydration of tertiary alcohols is reported. Performed in dichloromethane at room temperature, this reaction is readily tolerated by a broad scope of substrates, yielding alkenes preferentially with the (E)-geometry. While formation of the Hofmann products is generally favored, a dramatic change in alkene selectivity toward the Zaitzev products is observed when the reaction is carried out in dichloroethane at reflux.
Palladium-catalyzed 1,1-difunctionalization of ethylene
Saini, Vaneet,Sigman, Matthew S.
supporting information; experimental part, p. 11372 - 11375 (2012/08/29)
The 1,1-difunctionalization of ethylene, with aryl/vinyl/heteroaryl transmetalating agents and vinyl electrophiles, is reported. The reaction is high-yielding under a low pressure of ethylene, and regioselectivity is generally high for the 1,1-disubstituted product. The process is highlighted by the use of heteroaromatic cross-coupling reagents, which have not been competent reaction partners in previously reported efforts.
Copper-catalyzed alkene arylation with diaryliodonium salts
Phipps, Robert J.,McMurray, Lindsay,Ritter, Stefanie,Duong, Hung A.,Gaunt, Matthew J.
supporting information; experimental part, p. 10773 - 10776 (2012/08/07)
Alkenes and arenes represent two classes of feedstock compounds whose union has fundamental importance to synthetic organic chemistry. We report a new approach to alkene arylation using diaryliodonium salts and Cu catalysis. Using a range of simple alkenes, we have shown that the product outcomes differ significantly from those commonly obtained by the Heck reaction. We have used these insights to develop a number of new tandem and cascade reactions that transform readily available alkenes into complex arylated products that may have broad applications in chemical synthesis.
Alkene Hydrofunctionalization Reactions
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Page/Page column 11-13, (2009/04/24)
A reductive cross coupling reaction process for functionalization of a nucleophilic alkene can be achieved. The nucleophilic alkene and a nucleophilic cross coupling partner compound can be reacted in the presence of an oxidizable alcohol and a suitable catalyst to form a reductive coupling product. Various additives can also be useful to refine the process such as by mitigating certain undesirable intermediates, facilitating specific site selectivity for various substitutions or reaction sites, etc. Chiral additives can be optionally used which act to provide asymmetric catalysis, e.g. allow for regioselective and stereoselective production of reductive coupling products. A reductive cross coupling pathway can include oxidizing the oxidizable alcohol to form a catalyst hydride. The nucleophilic alkene can be inserted into the catalyst hydride to form a catalyst-alkyl intermediate. Further, the catalyst-alkyl intermediate can be transmetallized with the nucleophilic cross coupling partner compound to form a transmetallated intermediate. The catalyst can be reductively eliminated to form the reductive coupling product and a reduced catalyst. Finally, the reduced catalyst can be oxidized under aerobic conditions, for example with oxygen, to form the oxidized catalyst and subsequent repetition through the cyclic pathway.
Aerobic alcohol oxidation coupled to palladium-catalyzed alkene hydroarylation with boronic esters
Iwai, Yasumasa,Gligorich, Keith M.,Sigman, Matthew S.
, p. 3219 - 3222 (2008/12/23)
(Chemical Equation Presented) An oxidation exercise: An aerobic alcohol oxidation coupled with a regioselective palladium-catalyzed reductive functionalization of styrenes and arylboronic esters has been developed (see scheme). The mechanism is thought to proceed by initial oxidation of the solvent to generate a PdII-hydride species, which subsequently reacts with the alkene and arylboronic ester to ultimately generate a new C-C bond.
SYNTHESIS OF FUSED CYCLOPROPANES FROM γ-STANNYL ALCOHOLS
Kadow, John F.,Johnson, Carl R.
, p. 5255 - 5258 (2007/10/02)
Fused cyclopropanes including 3-carene and isosequicarene have been prepared by treatment of γ-stannyl alcohols with thionyl chloride.
Synthesis and Ring Cleavage of Highly Substituted 1,1-Dichloro- and 1-Bromo-1-fluorocyclopropanes
Anke, Lutz,Reinhard, Detlef,Weyerstahl, Peter
, p. 591 - 602 (2007/10/02)
The tri- and tetrasubstituted olefines 1, 2, 4, 7 - 15, and 19 react with CCl2 to give the dichlorocyclopropanes 22, 23, 25, 26a - 30a, and 33a - 37a in high yield, while the highly sterically hindered olefins 5, 6, and 21 show no reaction.In a few border
