110659-58-0Relevant articles and documents
Improved procedure for the synthesis of enantiomerically enriched cyclopropylmethanol derivatives
Charette,Prescott,Brochu
, p. 1081 - 1083 (1995)
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Asymmetric cyclopropanation of allylic alcohols employing sulfonamide/schiff base ligands
Balsells, Jaume,Walsh, Patrick J.
, p. 5005 - 5008 (2000)
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Highly efficient asymmetric simmons-smith cyclopropanation promoted by chiral heteroorganic aziridinyl ligands
Rachwalski, Michal,Kaczmarczyk, Sylwia,Lesniak, Stanislaw,Kielbasinski, Piotr
, p. 873 - 875 (2014)
Enantiomerically pure heteroorganic catalysts, bearing a hydroxy moiety, a stereogenic sulfinyl group, and a chiral aziridine moiety, have proved highly efficient in the asymmetric Simmons-Smith cyclopropanation of allylic alcohols, which generates the desired products in high yields (up to 95 %) and with ee values up to 94 %. The effect of the stereogenic centers at the sulfinyl sulfur atom and in the aziridine moiety on the stereochemical course of the title reaction is discussed. Combination at its best: Enantiomerically pure heteroorganic ligands, bearing a hydroxy moiety, a stereogenic sulfinyl group, and an enantiomeric aziridine moiety, have proved highly efficient in the asymmetric Simmons-Smith cyclopropanation of allylic alcohols, which generates the desired products in high yields (up to 95 %) and with ee values up to 94 %.
Catalytic, Enantioselective Cyclopropanation of Allylic Alcohols. Substrate Generality
Denmark, Scott E.,O'Connor, Stephen P.
, p. 584 - 594 (1997)
Catalytic, enantioselective cyclopropanation of a broad range of allylic alcohols and one homoallylic alcohol was carried out. The cyclopropanation reagent employed was bis(iodomethyl)zinc generated by the method of Furukawa, and the chiral promoter used (10 mol %) was the N,N-bis-(methanesulfonyl) derivative of (R,R)-1,2-diaminocyclohexane. Three experimental features were found to be critical for the rapid and selective cyclopropanation: (1) use of the ethylzinc alkoxide of the allylic alcohol as the substrate by prior deprotonation of the allylic alcohols by diethylzinc, (2) the formation of the zinc complex of the promoter by prior deprotonation of the bis-sulfonamide with diethylzinc, and (3) the use of added zinc iodide generated in situ from diethylzinc and iodine. The stereoselectivity of cyclopropanation was found to be independent of olefin geometry and worked well for substrates bearing both aliphatic and aromatic substituants at either or both 3-positions of the allylic alcohol. However, a methyl substituent on the 2-position of the allyl alcohol was not well tolerated and led to slow reactions and poor enantioselectivities. A rationale for the observed selectivities is proposed.
Iodomethylzinc phosphates: Powerful reagents for the cyclopropanation of alkenes
Lacasse, Marie-Christine,Poulard, Cyril,Charette, Andre B.
, p. 12440 - 12441 (2005)
A new family of zinc carbenoids derived from phosphoric acids was developed and used in the cyclopropanation of allylic alcohols and ethers and also of unfunctionalized olefins. The use of the chiral phosphoric acid of a 3,3′-disubstituted BINOL leads to efficient stereocontrol, affording the cyclopropanes of allylic and homoallylic ethers with complete conversions and up to 93% ee. A catalytic version of this reaction using 10 mol % of the chiral phosphate reagent is also disclosed. Copyright
Skeletally Tunable Seven-Membered-Ring Fused Pyrroles
Andreou, Dimitrios,Essien, Nsikak B.,Pubill-Ulldemolins, Cristina,Terzidis, Michael A.,Papadopoulos, Athanasios N.,Kostakis, George E.,Lykakis, Ioannis N.
supporting information, p. 6685 - 6690 (2021/09/11)
We describe a copper-mediated method that enables the synthesis of seven-membered-ring fused pyrroles (7-mrFPs). The protocol proceeds via an in situ spiro-intermediate ring expansion and tolerates a library of 7-mrFP derivatives with a broad range of functional groups in a simple step with tangible parameters and substrate adaptations. These rare 7-mrFPs are now accessible on a millimolar scale, and selected examples exhibit high antioxidant activity.
Donor-Acceptor Bicyclopropyls as 1,6-Zwitterionic Intermediates: Synthesis and Reactions with 4-Phenyl-1,2,4-triazoline-3,5-dione and Terminal Acetylenes
Potapov, Konstantin V.,Denisov, Dmitry A.,Glushkova, Valeriia V.,Novikov, Roman A.,Tomilov, Yury V.
, p. 15562 - 15576 (2020/11/30)
The bicyclopropyl system activated by incorporation of donor and acceptor groups in the presence of Lewis acids was used as a synthetic equivalent of 1,6-zwitterions. Opening of both cyclopropane rings in 2′-aryl-1,1′-bicyclopropyl-2,2-dicarboxylates (D-A bicyclopropyl, ABCDs) in the presence of GaI3 + Bu4N+GaI4- results in 5-iodo-5-arylpent-2-enylmalonates as products of HI formal 1,6-addition to the bicyclopropyl system. The use of GaCl3 or GaBr3 as a Lewis acid and terminal aryl or alkyl acetylenes as 1,6-zwitterion interceptors allows the alkyl substituent to be grown to give the corresponding acyclic 7-chloro(bromo)-hepta-2,6-dienylmalonates. The reaction of ABCDs with 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD) catalyzed by Yb(OTf)3 also results in the opening of both cyclopropane rings. The reaction products are tetrahydropyridazine derivatives - (7,9-dioxo-1,6,8-triazabicyclo[4.3.0]non-3-en-2-ylmethyl)malonates - containing one more PTAD moiety in the malonyl group.
Controlled Reduction of Carboxamides to Alcohols or Amines by Zinc Hydrides
Ong, Derek Yiren,Yen, Zhihao,Yoshii, Asami,Revillo Imbernon, Julia,Takita, Ryo,Chiba, Shunsuke
supporting information, p. 4992 - 4997 (2019/03/13)
New protocols for controlled reduction of carboxamides to either alcohols or amines were established using a combination of sodium hydride (NaH) and zinc halides (ZnX2). Use of a different halide on ZnX2 dictates the selectivity, wherein the NaH-ZnI2 system delivers alcohols and NaH-ZnCl2 gives amines. Extensive mechanistic studies by experimental and theoretical approaches imply that polymeric zinc hydride (ZnH2)∞ is responsible for alcohol formation, whereas dimeric zinc chloride hydride (H?Zn?Cl)2 is the key species for the production of amines.
