Hydroxy ammonium salts quaternary

A new ionic polymeric polycarbamate was synthesized after steps of polyurethane chemistry using 3-iso-cyanatemethyl-3,5,5-trimethylcyclohexyl isocyanate, 2,5-dimethyl-2,5-dihydroperoxyhexane, 1,6-butanediol, 2,4-tolylenediisocyanate, and N,N -bis(j3-Hydroxy-ethyOpiperazine [27]. Modification of the nitrogen of the piperazine ring into quaternary ammonium salt by treatment with methyliodide gave the MPI high electroconductivity. 

The reaction of 5-[2-(iV,./V-dimethylamino)ethyl]-l,2,4-oxadiazole with methyl iodide forms the quaternary ammonium salt 170 (Scheme 22), which undergoes elimination in the presence of base (diisopropylethylamine (DIEA), TEA, l,8-diazabicyclo[4.3.0]undec-7-ene, etc.) to form an intermediate 5-vinyl-l,2,4-oxadiazole 171, which undergoes in situ Michael addition with nucleophiles to furnish the Michael adducts 172. As an example, also shown in Scheme 22, 3-hydroxy-pyrrolidine allows the synthesis of compound 172a in 97% yield. Mesylation followed by deprotonation of the 1,2,4-oxadiazole methylene at C-5 enables Sn2 displacement of the mesylate to give the 5-azabicycloheptyl derivative 173, which is a potent muscarinic agonist <1996JOC3228>. 

M. Horikawa, J. Bush-Petersen, E. J. Corey, Enantioselective Synthesis of P-Hydroxy-a-amino Acid Esters by Adol Coupling Using a Chiral Quaternary Ammonium Salt as Catalyst , Tetrahedron Lett. 1999, 40, 3843-3846. 

One-pot conversions of 2-hydroxy(acylbenzenes) with anhydrides or acid chlorides to produce coumarins [52-54] and flavones [54-58] under mild liquiddiquid or solidtliquid two-phase conditions via a Baker-Venkataraman type reaction (Scheme 6.19) are catalysed by quaternary ammonium salts. 3-Substituted coumarins are produced from salicylaldehyde and malonodinitrile, or substituted acetonitriles, in high yield (>85%) in a one-pot catalysed sequential aldol-type reaction and cycliza-tion in the absence of an added organic solvent [59]. When 2 -hydroxychalcones are reduced under catalytic two-phase conditions with sodium borohydride, 2,4-cis-flavan-4-ols are produced [60] (see Section 11.3). 

Hydroxy ketones also give primarily syn 1,3-diols when chelates prepared with BC13 are reduced with quaternary ammonium salts of BH4 or BH3CN-.88... 

Maruoka and coworkers designed a new and highly efficient chiral N-spiro-type quaternary ammonium salt (S)-70 with dual functions for the asymmetric epoxidation of various enone substrates (Scheme 5.44) [45]. The exceedingly high asymmetric induction is ascribable to the molecular recognition ability of the catalyst toward enone substrates by virtue of the appropriately aligned hydroxy functionality, as well as the chiral molecular cavity. Indeed, the observed enantioselectivity depends heavily... 

Another class of carbonyl-containing substances are the quinones. Quinone (263) shows pure carbonyl behaviour by adding chlorotrimethylsilane (142) in presence of a quaternary ammonium salt to form l-chloro-2-hydroxy-5-trimethylsiloxyben-zene (264)172 in a 1,4-addition-type reaction. 

The reaction of carbonyl substrates with oxygen in basic media has been utilized by Shioiri and co-workers to generate optically active a-hydroxy carbonyl compounds when a quaternary ammonium salt such as /V-(4-trifluoromethylphenylmethyl)cinchoninium bromide (2) is employed as a chiral catalyst102. Enantiomeric excesses up to 74% have been realized by using this simple methodology (Table 10). 

The ring-closure mechanism of 2-chloroethanol has been studied on the basis of kinetic and equilibrium chlorine isotope effects. Epoxidation of the terminal double bond of farnesyl acetate has been achieved via the bromohydrin, obtained with NBS. A stereospecific method has been elaborated for the preparation of 1-alkynyloxiranes, starting from the monotosylate ester of acetylenic diols. 1-Alkynyloxiranes are also formed from a-hydroxy quaternary ammonium salts in alkaline medium (Eq. 57). ... 

Cetyltrimethylammonium permanganate (CTAP), a stable quaternary ammonium salt, provides a valuable modification of the original permanganate procedure for selective conversion of substrates containing alkenic and hydroxy groups. Yields are good to excellent (Scheme 44) and large quantities of substrate can be transformed. 

As mentioned above, quaternary ammonium salts derived from cinchona alkaloids have occupied the central position as efficient PTCs in various organic transformations, especially in the asymmetric a-substitution reaction of carbonyl derivatives. A cinchona alkaloidal quaternary ammonium salt, which acts as a PTC in various organic reactions, is prepared by a simple and easy chemical transformation of the bridgehead tertiary nitrogen with a variety of active halides, mainly arylmethyl halides. Other moieties of cinchona alkaloids (the 9-hydroxy, the 6 -methoxy, or the 10,11-vinyl) are occasionally modified for the enhancement of both chemical and optical yields (Figure 6.4). 

As shown in Scheme 8.2, chiral P-hydroxy-a-amino adds can be obtained by the Mukaiyama-type aldol reaction of aldehydes with glycine-derived enol silyl ethers using cinchona-based quaternary ammonium salts. In 2004, Castle and coworkers [9] found that dnchona-based quaternary ammonium salts such as 13 are also able to catalyze the dired aldol readion of aldehydes with the glydne donor 14 in the presence of a phosphazene base such as BTTP (t-butyliminotri(pyrrolidino)phos-... 

Acrylic acid was first attached to tlie hydroxy-modified solid support via an ester bond to yield 73. This was followed by a Michael addition to give the tertiary amine 74. Alkylation led to the quaternary ammonium salt 75, which is suitably predisposed for 3-eliniination induced by Huenig s base, thereby yielding the required tertiary amine. 

Addition of vinyllithium to 441 gives 442 as a mixture of syn and anti diols. The beauty of this synthesis is that both the syn and the -diol stereoisomers rearrange to the same tetra-hydrofuran product. Thus, acetal 443 undergoes a Prins pinacol rearrangement to tetra-hydrofuran 444 upon treatment with SnCU in nitromethane. The transformation proceeds with complete preservation of enantiomeric purity. Baeyer—Villiger reaction stereospecifically introduces the 3-hydroxy substituent, and conversion to the quaternary ammonium salt completes the target molecule 446. 

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