934219-63-3Relevant academic research and scientific papers
Palladium-Catalyzed Allyl-Allyl Reductive Coupling of Allylamines or Allylic Alcohols with H2as Sole Reductant
Zhou, Xibing,Zhang, Guoying,Huang, Renbin,Huang, Hanmin
supporting information, p. 365 - 369 (2021/01/26)
Catalytic carbon-carbon bond formation building on reductive coupling is a powerful method for the preparation of organic compounds. The identification of environmentally benign reductants is key for establishing an efficient reductive coupling reaction. Herein an efficient strategy enabling H2 as the sole reductant for the palladium-catalyzed allyl-allyl reductive coupling reaction is described. A wide range of allylamines and allylic alcohols as well as allylic ethers proceed smoothly to deliver the C-C coupling products under 1 atm of H2. Kinetic studies suggested that the dinuclear palladium species was involved in the catalytic cycle.
Development of an intramolecular aryne ene reaction and application to the formal synthesis of (±)-crinine
Candito, David A.,Dobrovolsky, Dennis,Lautens, Mark
supporting information, p. 15572 - 15580 (2012/11/07)
A general and high yielding annulation strategy for the synthesis of various carbo- and heterocycles, based on an intramolecular aryne ene reaction is described. It was found that the geometry of the olefin is crucial to the success of the reaction, with exclusive migration of the trans-allylic-H taking place. Furthermore, the electronic nature of the aryne was found to be important to the success of the reaction. Deuterium labeling studies and DFT calculations provided insight into the reaction mechanism. The data suggests a concerted asynchronous transition state, resembling a nucleophilic attack on the aryne. This strategy was successfully applied to the formal synthesis of the ethanophenanthridine alkaloid (±)-crinine.
Intramolecular aryne-ene reaction: Synthetic and mechanistic studies
Candito, David A.,Panteleev, Jane,Lautens, Mark
, p. 14200 - 14203 (2011/10/31)
Although the chemistry of arynes is well developed, some challenges still remain. The ene reaction of arynes has not gained widespread use in synthesis as a result of poor yields and selectivity. A general, high yielding and selective intramolecular aryne-ene reaction is described providing various benzofused carbo- and heterocycles. Mechanistic data is presented, and a rationale for the resulting stereochemistry is discussed.
Enantioselective Claisen rearrangements with a hydrogen-bond donor catalyst
Uyeda, Christopher,Jacobsen, Eric N.
supporting information; body text, p. 9228 - 9229 (2009/02/03)
N,N-Diphenylguanidinium ion associated with the noncoordinating BArF counterion is shown to be an effective catalyst for the [3,3]-sigmatropic rearrangement of a variety of substituted allyl vinyl ethers. Highly enantioselective catalytic Claisen rearrangements of ester-substituted allyl vinyl ethers are then documented using a new C2-symmetric guanidinium ion derivative. Copyright
Stereoselective reductions of N-Boc-hexahydro-1H-indolin-5(6H)-ones
Brodney, Michael A.,Cole, Marcus L.,Freemont, Jamie A.,Kyi, Stella,Junk, Peter C.,Padwa, Albert,Riches, Andrew G.,Ryan, John H.
, p. 1939 - 1943 (2007/10/03)
We report the divergent effects of a 3a-methyl and 3a-phenyl substituent on the chemoselectivity and stereoselectivity of reduction of the enamide moiety of N-Boc-hexahydro-1H-indolin-5(6H)-ones. Under ionic reduction conditions (triethylsilane/trifluoroacetic acid) the enamide group of 3a-methyl-N-Boc-hexahydro-1H-indolin-5(6H)-one was reduced to afford exclusively a cis ring-fused product. For the 3a-phenyl substituted analogue more forcing conditions (sodium cyanoborohydride at pH 2-2.5) were required and resulted in the selective reduction of the enamide group to give a trans ring-fused product as well as reduction of the ketone group.
