3-amino-1-alkene 2-alkenal

A related cyclization of N-sulfonyl-amino-alkenes and NBS gave the bromo-lactam, " and a dichloro-Af,7/-bisallylamide was converted to a dichloro-lactam with FeCl2. ... 

In a related approach, John Wolfe of the University of Michigan has demonstrated (Angew. Chem. Inl.Ed. 2004,43,3605) that Heck addition of an aryl halide 5 to an amino alkene 6 can be terminated by C-N bond formation. The reaction proceeds with high diastereoselectivity, to give 7. 

Intramolecular hydroamination of amino alkenes.1 This lanthanide effects cy-clization of amino alkenes in hydrocarbon solvents to five- and six-membered nitrogen heterocycles. 

G. Laban and R. Mayer, Praparative Methoden zur Darstellung N,N-disubstituierter 1-Amino-alkene-(l) (Aldehydenamine) , Z. Chem., 8, 165-170 (1968). 

A new procedure for GSL synthesis via olefin cross metathesis (164) is highly versatile in terms of the hydrophobic agly-cone. A protected 5 carbon amino alkene diol is the central building block to which the protected carbohydrate donor, long chain fatty acid, or, by olefin cross metathesis, the long alkenyl chain of the base can be coupled, in a variety of sequences. This atypical synthetic flexibility should allow a stmctural approach to dissecting the role of the lipid moiety in GSL receptor function and intracellular trafficking. 

A related cyclization of A-sulfonyl-amino-alkenes and NBS gave the bromo-... 

The organolanthanide-catalyzed alkene hydroamination has been reported. With this approach, amino alkenes (not enamines) can be cyclized to form cyclic amines, and amino alkynes lead to cyclic imine. The use of synthesized C-1 and C-2 symmetric chiral organolanthanide complexes give the amino alcohol with good enantioselectivity. 

Intramolecular cyclization is a general reaction in the anodic oxidation of substituted amino alkenes. Thus, the already mentioned A-methyl-A-phenyl-1,2,2-triphe-nylvinylamine leads to a new 3/7-indole by anodic oxidation in the presence of 2,6-lutidine [149,150]. The corresponding enediamine undergoes an electrolytic double cyclization to form an indolooxazolidine [149]. The formation of isoquinolines, benzaze-pines, and tetrahydrocarbazoles may also be obtained by anodically initiated intramolecular cyclization of A-benzyl, A- S-phenethyl, and anilino enaminones [Eq. (30)] [158]. 

Amino alkenes such as H2NCH2CHjChUCH=CHj are catalytically converted to five-membered heterocycles by [(MejCjUsl LaH),. Give the steps of (he reaction sequence and incorporate them into a Tolman catalytic cycle. Present arguments against formation of an La-alkene bond. (See Gagne. M. R. Marks. T. J. J. Am. Chem. Soc. 1989. III. 4108-4109.)... 

Products of addition to styrene double bonds can arise as a result of light induced electron transfer reactions. Lewis has studied the intramolecular reaction of l-phenyl-w-amino alkenes (422) 289,290 products arise from electron transfer from the amine nitrogen to the excited state of the styryl group followed by intramolecular proton transfer in the radical ion pair produced. The resultant biradical then couples to yield the isolated products (423) and (424). Sensitisation of the intermolecular analogue of this reaction by 1,4-dicyanobenzene has been reported and is proposed to occur by electron transfer from the styrene to the excited state of the sensitiser followed by attack of an amine on the styrene radical cation. This ultimately leads to the product of anti-Markovnikov addition of the amine across the double bond of the styrene. This is similar to the sequence long since established by... 

An intramolecular allyl silane/N-sulfonyl iminium ion cyclization has also been used as a pivotal step in an approach to the tricyclic core of the unique marine alkaloid sarain A [46]. The starting material was aziridine ester 129 (Scheme 25) which was elaborated to amide 130. An important step in the synthetic strategy was thermolysis of 130 to an azomethine ylide, which underwent stereospecific intramolecular 1,3-dipolar cycloaddition with the Z-alkene to produce bicyclic lactam 131 [47]. This compound was then elaborated into allyl silane 132. It was then possible to replace the lactam N-benzyl functionality with a tosyl moiety, leading to 133, and subsequent reduction of the carbonyl group afforded the desired cyclization precursor a-hydroxy sulfonamide 134. Exposure of 134 to ferric chloride promoted cyclization to a single stereoisomeric tricyclic amino alkene 136 having the requisite sarain A nucleus. It is believed that the intermediate N-sulfonyl iminium ion cyclizes via the conformation shown in 135. 

An early example of a natural product synthesis featuring an indole C-H bond alkenylation was report by Trost and co-workers (Scheme 54). Using stoichiometric Pd(II)-salts in combination with silver tetrafluoroborate, they were able to mediate a oxidative Heck process onto the bicyclic amino-alkene. Using a reductive work-up to reduce the Pd-C bond, they were able to complete a synthesis of ibogamine [76]. 

Aminobenzimidazoles, quaternized with l-bromoprop-2-yne and converted with ammonia into the 2-imines, cyclize on heating with a strong base the quaternary salt behaves similarly. The enzyme catalase promotes the cyclization of the amino-alkene (12.5) to a benzimidazole under comparatively mild conditions (review [B-53]). 

Amino-alkene werdennur in AusnahmefallenunddannmitRaney-Nickel1 oderPal-ladium-Katalysatoren2 erhalten. Platin katalysiert primar die selektive Absattigung der C=C-Dopp elbindung. 

Finally, in Wander s synthesis of the hexacyclic himandrin skeleton, amino-alkene 100 was oxidized to its corresponding methyl ketone, which was trapped by nucleophilic addition of the amine.7 Dehydration of the adduct then delivered enamine 100, which possessed all six rings of the himandrine skeleton. 

The remarkable effect of substituents on regioselectivity was observed in the intermolecular reaction of 1-substituted 2,3-butadien-l-ols with nucleophiles giving different regioisomers depending on the kind of 1-substituents. l-Phenyl-2,3-butadien-l-ol (383) reacts with diethylamine to afford 2-amino-1,3-diphenyl-3-buten-l-ol 384 regio- and stereoselectively. On the other hand, reaction of 1-alkyl-2,3-butadien-l-ol 385 yields the 4-amino-2( )-alken-l-ol 386. These reactions offer efficient synthetic methods for 2- or 4-amino alken-l-ols with high regio-and stereoselectivity [150]. 

In an effort to increase the potential for enantioinduction in the hydroamination of amino alkenes, bimetallic complexes of Zn (73) and Mg (74) have been prepared... 

For a recent example of enantioselective intra- and intermolecular hydroaminations of terminal amino-alkenes and styrene derivatives with heteroleptic chiral magnesium-phenolate complexes, see Emge, T. J. Hultzsch, K. C. Angew. Chem. Int. Ed 2012, 51, 394. 

Cyclic secondary amines are also produced by the ring expansion of O-sulphonyloximes via a Beckmann rearrangement/ the cyclization of a,aliphatic diamines by a ruthenium catalyst/ the palladium-promoted ring closure of amino-alkenes/ and the sulphonamidomercuration of 1,4- and 1,5-dienes. The latter two reactions form part of a wealth of new literature on the amination of olefins and acetylenes via aminomercuration " and via palladium catalysis. ... 

Picosecond spectroscopy sheds some light on the electron transfer behavior of the binuclear ion [(CN)5Fe(II)CNCo(III)(hedta)] ". Excited-state electron transfer takes place on a very short time scale giving iron(III) and cobalt(II) which undergoes a spin change and the back reaction is characterized by a 95-ps lifetime. The coordination of copper(I) to the olefinic chromophore of cobalt(III)-bound amino-alkene ligands results in binuclear complexes (1) which undergo intramolecular electron transfer... 

BromocycUzation reactions are well known for their ability to facilitate the construction of chiral compounds. An example this chemistry outlined the preparation of tetrahydropyrroles (Scheme 3.13) [13]. A chiral phosphoric acid was used to provide the stereocontrol, and NBS served as the bromine source. Using this system, a range of gamma-amino alkenes were converted into nitrogen heterocycles in high yield with moderate to good selectivity. 

YoshiakiNishibayashi of the University of Tokyo devised (Angew. Chem. Int. Ed. 2009, 48, 2534) Ru catalysts for the cyclization of an enyne such as 21 to the cyclohexadiene 22. Laurel L. Schafer of the University of British Columbia developed (/. Am. Chem. Soc. 2009,131, 2116) a Zr catalyst for the diastereocontro lied cyclization of amino alkenes such as 23. Hongbin Zhai of the Shangahi Institute of Organic Chemistry showed (J. Org. Chem. 2009, 74, 2592) that the Mo-mediated cyclization of 25 also proceeded with high diastereocontrol. Even more impressive was the selectivity Kozo Shishido of the University of Tokushima demonstrated (Tetrahedron Lett. 2009, 50, 1279) for the cyclization of 27. 

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