Allyl Amine Derivatives

An important variant for transition metal-catalyzed carbon-nitrogen bond formation is allylic substitution (for reviews, see1,la lh). Nucleophilic attack by an amine on an 7r-allyl intermediate, generated from either an allylic alcohol derivative,2 16,16a 16f an alkenyloxirane,17-19,19a-19d an alkenylaziridine19,19a 19d, or a propargyl alcohol derivative,21,21a 21d gives an allylic amine derivative. 

Similarly, both acyclic and cyclic allyl amine derivatives have been applied in 1,3-dipolar cycloadditions (134-138). Langlois et al. (139) used a,()-unsaturated-y-lactams derived from (5)-pyroglutaminol, such as 91 and 92, in the 1,3-dipolar cycloaddition with the A -benzylnitrone derived from formaldehyde (Scheme 12.30). For compound 91, one of the 1,3-dipolar cycloaddition product isomers obtained... 

We found that under the conditions of the Wacker oxidation,27 the terminal double bonds of the metathesis products were cleanly transformed to the corresponding aldehydes. While the regioselective oxidation of protected allylic alcohols has been reported,28 the selective Wacker oxidation of an allylic amine derivative to the aldehyde is unprecedented. The Ns protected precursor 19 produced only the starting amine (NsN(H)CH2CH2CH2CH(OEt)2). Consequently, the Ns protecting groups were exchanged with Cbz (27) which successfully led to the desired aldehyde 28. 

Lithiated allyl sulfides (in common with allyl sulfoxides and selenides, but in contrast with allyl ethers and allyl amine derivatives) tend to react with alkyl halides at the a position, adjacent to S.1 The best a-selectivities are obtained with lithium-coordinating S-substituents such as pyridyl (114),85 imidazolyl (115), and dimethylaminocarbonyl (116).1... 

Isomerization. A -Tosylazetidines undergo ring opening to afford the isomeric allylic amine derivatives. ... 

Yasuda obtained membranes with good reverse osmosis properties by polymerizing gas plasma mixtures of acetylene/water/nitrogen and acetylene/wa-ter/carbon monoxide.92 9J Elemental analysis of the acetylene/water/nitrogen membrane was not given, but it was likely approximately equivalent to the allyl-amine-derived composition. Yasuda has observed membrane performance levels as high as 99% salt rejection and 38 gfd, tested on 3.5% sodium chloride at 1,500 psi. 

A synthesis of Agelastatin A by Weinreb and co-workers featured the use of a 13 bis[2-(trimethylsilyl)ethylsuifonyl] sulfodiimide 137 2 as an enophile in a two-step allylic amination reaction [ heme 8.137]. The initial ene reaction produced a dipolar intermediate 1373 that underwent a [2,3] Sigmatropic shift to afford the SES-protected allylic amine derivative 137,4. Reductive cleavage of the N-S bond followed by cleavage of the Boc group with trifluoroacetic acid gave the sulfonamide 1373 in 50-60% overall yield. Final deprotection of the SES group with TBAF returned the desired amine 137,6 in 90% yield. 

More recently, to find more effective methods to construct bis(heterocycle)s containing a pyrimidine ring from MBH derivatives, the solid-phase parallel synthesis of new annulated pyrimidinone derivatives was disclosed (Scheme 4.219). " The resin-bound allyl amine derivatives 742 were treated with cyanogen bromide to yield the pyrazole derivatives 743 in good yields under standard conditions. The subsequent lactonization with cleavage of the resin afforded the pyrimidinone derivative 744 in good yields in the presence of 20% triethylamine in chloroform under reflux. 

The allylic amine derivative (27) was used to prepare three of the four diastereomers of 3-amino cyclopentane-1,2-diol, with the remaining one being made from the readily available epoxide... 

Mechanistic smdies of Pd(MeCN)2Cl2-catalysed hydroalkylation reactions of allylic amine derivatives by n-BuZnBr in the presence of Zn(OTf)2, benzoquinone, and DMA suggested a reversible )3-hydride elimination/hydride insertion process leading to the primary Pd-alkyl intermediate, which underwent trans-metalation followed... 

A pigment dispersing agent is used that contains a poly(allyl-amine) derivative, a thermosetting binder and an organic solvent. The poly(allylamine) derivative can be obtained by reacting a poly-(allylamine) with a polyester or a polyamide. 

From Unsaturated Sugars. — Allylic rearrangement of ally cyanates, formed in situ from carbamates such as 24 (derived originally from o-glucal triacetate), yielded isocyanates, e.g. 25, that could then be converted to allylic amine derivatives, e.g. 26 (Scheme 6). Trapping of an allylic... 

Compound (1) has been utilized in the total synthesis of gaha-culine (6). Upon treatment with (1), alkene (3) afforded a mixture of allylic amine derivatives (4) and (5) in 45% yield (eq 4). Compound (1) has also been used effectively in the syntheses of both j3-apopicropodophyllin analogs and daunosamine analogs. ... 

Fig. 5.2 Reactive conformations in catalyzed and 9-BBN by hydroboration of N-tosyl-protected allylic amine derivatives, a Preferential orientation in catalyzed hydroboration of n-tosyl-protected allylic amine derivatives, b Preferential orientation in 9-BBN hydroboration of N-tosyl-protected allylic amine substrate (R = i-Pr)...

Other annellated tetrahydropyranes have been prepared by a hydroformylation-allylboration-hydroformylation sequence (Scheme 5.84) [76]. By treatment of an allyl amine derivative with syngas, a cascade reaction was initiated consisting of hydroformylation and hemiacetal formation, followed by a second hydroformylation-hemiacetal formation step. The product was converted via Ley-Griffith oxidation into the corresponding lactone. 

Scheme 5.113 Hydroaminomethylation of an allyl amine derivative using urea as source for ammonia.

Alternative approach to 4,5,6,7-tetrafluoroindole nitrogen modification was proposed by Trost et al. Reaction of 4,5,6,7-tetrafluoroindole 132 with vinyl azyridines 166 under Pd2(dba)3 catalysis proceeded with ring-opening to give, stereoselec-tively, allyl amine derivatives 167 in high yields [61]. 

Stereoselective Arylation of IV-Protected Allylic Amine Derivatives... 

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