Categories: C-N Bond Formation > Amines >
Synthesis of 1,2-diamines
Indium tribromide catalyzes efficiently the aminolysis of activated aziridines with aromatic amines under mild reaction conditions to afford the corresponding vicinal-diamines in high yields with high selectivity.
J. S. Yadav, B. V. S. Reddy, K. Vishweshwar Rao, K. Saritha Raj, A. R. Prasad, Synthesis, 2002, 1061-1064.
A one-pot diamination of simple unactivated alkenes using an electrophilic nitrene source and amine nucleophiles provides rapid access to 1,2-vicinal diamines from terminal alkenes on good yield and regioselectivity. The transformation proceeds smoothly through a Rh(III)-catalyzed aziridination of alkenes with subsequent ring opening by primary or secondary amines.
S. Lee, Y. J. Jang, E. J. T. Phipps, H. Lei, T. Rovis, Synthesis, 2020, 52, 1247-1252.
Iodine catalyzes stereospecific 1,2-diaminations of unactivated alkenes. Depending on the nitrogen source and the configuration of the alkenes, two methods provide access to all disastereomeric forms of 1,2-diamines.
S. Minakata, H. Miwa, K. Yamamoto, A. Hirayama, S. Okumura, J. Am. Chem. Soc., 2021, 143, 4112-4118.
A chirally modified aryliodine(I) catalyst enables an enantioselective vicinal diamination of styrenes with conventional 3-chloroperbenzoic acid as the terminal oxidant.
K. Muńiz, L. Barreiro, R. M. Romero, C. Martínez, J. Am. Chem. Soc., 2017, 139, 4354-4357.
A rhodium-catalyzed hydroamination of primary and secondary allylic amines using diverse amine nucleophiles, including primary, secondary, acyclic, and cyclic aliphatic amines provides a wide range of unsymmetrical vicinal diamines. This methodology enables a the rapid synthesis of several bioactive molecules and analogs.
B. J. Lee, A. R. Ickes, A. K. Gupta, S. C. Ensign, T. D. Ho, A. Tarasewicz, E. P. Vanable, G. D. Kortman, K. L. Hull, Org. Lett., 2022, 24, 5513-5518.
A cationic iron complex catalyzes the aminolysis of meso-N-aryl aziridines very efficiently and furnishes valuable 1,2-diamines in excellent yields. This protocol is compatible with a range of functional groups both in the aziridine and amine components.
A. Marti, L. Richter, C. Schneider, Synlett, 2011, 2513-2516.
The aminolysis of meso-N-phenyl aziridines is efficiently catalyzed by 1 mol% of Sc(OTf)3 and furnishes valuable 1,2-diamines in good to excellent yields.
S. Peruncheralathan, M. Henze, C. Schneider, Synlett, 2007, 2289-2291.
SN2-type ring-opening of activated aziridines with 2-bromoanilines followed by a Pd-catalyzed intramolecular C-N bond formation enable a highly regio- and stereoselective route for the synthesis of racemic and nonracemic tetrahydroquinoxalines.
M. K. Ghorai, A. K. Sahoo, S. Kumar, Org. Lett., 2011, 13, 5972-5975.
Dinuclear iodine(III) reagents with a defined structure enable an intermolecular diamination of alkenes. These highly reactive hypervalent iodine(III) compounds are accessible through protolytic aminolysis events, which generate defined imido-iodine(III) groups.
C. Röben, J. A. Souto, E. C. Escudero-Adán, K. Muńiz, Org. Lett., 2013, 15, 1008-1011.
A catalytic asymmetric ring-closing 1,5-C-H amination of sulfamoyl azides provides chiral 1,2,5-thiadiazolidine-1,1-dioxides in up to 98% yield and up to 98% ee if the C-H bond is in a benzylic position. The reaction is catalyzed by a recently introduced simple chiral ruthenium bis(oxazoline) (pybox) complex.
X. Nie, Z. Yan, S. Ivlev, E. Meggers, J. Org. Chem., 2021, 86, 750-761.
The use of CuCl as catalyst and di-tert-butylthiadiaziridine 1,1-dioxide as nitrogen source allows an effective diamination of activated terminal olefins in good yields under mild reaction conditions.
B. Zhao, W. Yuan, H. Du, Y. Shi, Org. Lett., 2007, 9, 4943-4945.
An operationally simple iron-catalyzed difunctionalization of alkenes provides primary 2-azidoamines, which are versatile precursors to vicinal diamines. A wide array of alkene substrates are tolerated, including complex drug-like molecules and a tripeptide. Facile, chemoselective derivatizations of the azidoamine group demonstrate the versatility of this masked diamine motif.
S. Makai, E. Falk, B. Morandi, J. Am. Chem. Soc., 2020, 142, 21548-21555.
A regioselective intermolecular three-component reaction of styrenes with acetonitrile and azodicarboxylates provides vicinal diamination products in good yields via the Ritter reaction.
J. Cao, D. Lv, F. Yu, M.-F. Chiou, Y. Li, H. Bao, Org. Lett., 2021, 23, 3184-3189.
The use of a chiral pyridine-oxazoline ligand enables a palladium(II)-catalyzed asymmetric 1,2-diamination of 1,3-dienes with readily available dialkylureas at the terminal C-C double bond to provide 4-vinylimidazolidin-2-ones in high yields and with excellent levels of enantioselectivity.
M.-S. Wu, T. Fan, S.-S. Chen, Z.-Y. Han, L.-Z. Gong, Org. Lett., 2018, 20, 2485-2489.
Cu(I)-catalyzed diamination of conjugated dienes with di-tert-butyldiaziridinone as nitrogen source proceeds at the internal double bond with high regio- and diasteroselectivity in good yield using inexpensive CuBr as catalyst.
B. Zhao, X. Peng, S. Cui, Y. Shi, J. Am. Chem. Soc., 2010, 132, 11009-11011.
The use of di-t-butyldiaziridinone as nitrogen source and a N-heterocyclic carbene-Pd(0) complex as catalyst allows an efficient diamination of a wide variety of conjugated dienes and trienes in good yields with high regio- and stereoselectivities.
L. Xu, H. Du, Y. Shi, J. Org. Chem., 2007, 72, 7038-7041.
A wide variety of terminal olefins can be effectively diaminated at allylic and homoallylic carbons via formal C-H activation in good yields with high stereoselectivity using di-tert-butyldiaziridinone as nitrogen source and Pd(PPh3)4 as catalyst.
H. Du, W. Yuan, B. Zhao, Y. Shi, J. Am. Chem. Soc., 2007, 129, 7496-7497.
A catalytic asymmetric diamination of alkyl dienes using N,N′-di-tert-butylthiadiaziridine 1,1-dioxide in the presence of Pd(0) and a chiral phosphoramidite ligand gives cyclic sulfamides in high yield and high ee. The diamination is also amenable to gram scale.
R. G. Cornwall, B. Zhao, Y. Shi, Org. Lett., 2013, 15, 796-799.
A remarkable Pd-catalyzed diamination of unactivated alkenes using N-fluorobenzenesulfonimide (NFBS) as an aminating reagent is described. The reaction incorporates one nitrogen donor from the substrate and the other from the NFBS, thereby generating cyclic diamine derivatives in a single step. The products are differentially protected at both nitrogens, allowing for maximal synthetic flexibility.
P. A. Sibbald, F. E. Michael, Org. Lett., 2009, 11, 1147-1149.
A palladium-catalyzed intramolecular diamination reaction yields cyclic ureas as direct products of an oxidative alkene transformation in the presence of iodosobenzene diacetate as terminal oxidant.
J. Streuff, C. H. Hövelmann, M. Nieger, K. Muniz, J. Am. Chem. Soc., 2005, 127, 14586-14587.