105882-02-8Relevant articles and documents
A new selena-aza-payne-type rearrangement of aziridinylmethyl tosylates mediated by tetraselenotungstate
Sureshkumar, Devarajulu,Koutha, Srinivasamurthy,Chandrasekaran, Srinivasan
, p. 4543 - 4551 (2007)
Tetraselenotungstate 1 reacts with simple (N-tosylaziridinyl)-methyl tosylate derivatives to give allylamine derivatives as the only products by an unprecedented selena-aza-Payne-type rearrangement. When the methodology is extended to disubstituted (N-tos
Copper-Catalyzed Azide–Ynamide Cyclization to Generate α-Imino Copper Carbenes: Divergent and Enantioselective Access to Polycyclic N-Heterocycles
Chen, Yang-Bo,Deng, Chao,Liu, Rai-Shung,Liu, Xin,Luo, Chen,Wang, Ze-Shu,Ye, Long-Wu,Zhai, Tong-Yi,Zhang, Yi-Ping
, p. 17984 - 17990 (2020/08/21)
Here an efficient copper-catalyzed cascade cyclization of azide-ynamides via α-imino copper carbene intermediates is reported, representing the first generation of α-imino copper carbenes from alkynes. This protocol enables the practical and divergent synthesis of an array of polycyclic N-heterocycles in generally good to excellent yields with broad substrate scope and excellent diastereoselectivities. Moreover, an asymmetric azide–ynamide cyclization has been achieved with high enantioselectivities (up to 98:2 e.r.) by employing BOX-Cu complexes as chiral catalysts. Thus, this protocol constitutes the first example of an asymmetric azide–alkyne cyclization. The proposed mechanistic rationale for this cascade cyclization is further supported by theoretical calculations.
Rh(III)-Catalyzed C-H Activation-Initiated Directed Cyclopropanation of Allylic Alcohols
Phipps, Erik J.T.,Rovis, Tomislav
, p. 6807 - 6811 (2019/05/10)
We have developed a Rh(III)-catalyzed diastereoselective [2+1] annulation onto allylic alcohols initiated by alkenyl C-H activation of N-enoxyphthalimides to furnish substituted cyclopropyl-ketones. Notably, the traceless oxyphthalimide handle serves three functions: Directing C-H activation, oxidation of Rh(III), and, collectively with the allylic alcohol, in directing cyclopropanation to control diastereoselectivity. Allylic alcohols are shown to be highly reactive olefin coupling partners leading to a directed diastereoselective cyclopropanation reaction, providing products not accessible by other routes.
Rhodium/Yanphos-Catalyzed Asymmetric Interrupted Intramolecular Hydroaminomethylation of trans-1,2-Disubstituted Alkenes
Chen, Caiyou,Jin, Shicheng,Zhang, Zhefan,Wei, Biao,Wang, Heng,Zhang, Kai,Lv, Hui,Dong, Xiu-Qin,Zhang, Xumu
, p. 9017 - 9020 (2016/08/05)
The first interrupted asymmetric hydroaminomethylation reaction was developed. The challenging trans-1,2-disubstituted olefins were employed as substrates, and a series of valuable chiral pyrrolidinones and pyrrolidines were obtained in high yields with high regioselectivities and excellent enantioselectivities. Several synthetic transformations were conducted, demonstrating the high synthetic utility of our method. A creative route for the synthesis of vernakalant and Enablex was also developed.
Bicyclic cyclopentenones via the combination of an iridium-catalyzed allylic substitution with a diastereoselective intramolecular pauson-khand reaction
Farwick, Andreas,Engelhart, Jens U.,Tverskoy, Olena,Welter, Carolin,Umlauf Nee Stang, Quendolin A.,Rominger, Frank,Kerr, William J.,Helmchen, Guenter
experimental part, p. 349 - 370 (2011/04/18)
Enantioselective syntheses of bicyclic cyclopentenones are described. Key steps are an iridium-catalyzed allylic substitution and an intramolecular diastereoselective Pauson-Khand reaction. The diastereoselectivity of the Pauson-Khand reaction was found t
Copper-catalyzed N-Allenylation of allylic sulfonamides
Persson, Andreas K. A.,Johnston, Eric V.,Baeckvall, Jan-E.
supporting information; experimental part, p. 3814 - 3817 (2009/12/06)
Figur Presented Allylic allenic amides have been synthesized via a copper-catalyzed cross-coupling between allylic sulfonamides and bromoallenes in moderate to good yields. Copper(I) thiophene-2-carboxylate (CuTC) was used a source of copper with DMEDA as the ligand. The allenylated products obtained are potential substrates for palladium-catalyzed carbocyclizations.
ALLYLIC AMINATION OF ALKENES BY TOSYLIMINOIODOBENZENE : MANGANESE PORPHYRINS AS SUITABLE CATALYSTS
Mahy, J. P.,Bedi, G.,Battioni, P.,Mansuy, D.
, p. 1927 - 1930 (2007/10/02)
Manganese-porphyrins and particularly Mn(TPP)(ClO4) were found to be much better catalysts than iron-porphyrins for allylic N-tosylamination of alkenes by tosyliminoiodobenzene.With the former catalyst, cyclohexene was selectively transformed into 3-tosyl
Allylic Selenides in Organic Synthesis: New Methods for the Synthesis of Allylic Amines
Shea, Regan G.,Fitzner, Jeffrey N.,Fankhauser, John E.,Spaltenstein, Andreas,Carpino, Philip A.,et al.
, p. 5243 - 5252 (2007/10/02)
Oxidative rearrangement of allylic selenides in the presence of various amine nucleophiles provides synthetic access to a variety of allylic amine derivatives.The stereochemical outcome of these reactions has been investigated, and is consistent with a -sigmatropic rearrangement mechanism.Several D-α-amino acids and racemic β,γ-unsaturated α-amino acids were prepared in this manner.A variant of this process employing an achiral allylic selenide and chiral amide afforded protected allylic amines in low diastereoisomeric excess.
SYNTHESIS OF PROTECTED ALLYLIC AMINES FROM ALLYLIC PHENYL SELENIDES: IMPROVED CONDITIONS FOR THE CHLORAMINE T OXIDATION OF ALLYLIC PHENYL SELENIDES
Fankhauser, John E.,Peevey, Richard M.,Hopkins, Paul B.
, p. 15 - 18 (2007/10/02)
Anhydrous chloramine T in methanol is a highly effective reagent for the conversion of allylic phenyl selenides to the corresponding rearranged N-allylic-p-toluenesulfonamides.The reaction presumably proceeds via an allylic selenimide intermediate which undergoes -sigmatropic rearrangement.
