A -hydroxy-phthalimide

Fig. 32 OS supported oiganocatalysts tertiary amine, A -hydroxy-phthalimide and chiral pyrolidines...

A-hydroxy-phthalimide (NHPI) acts as a catalyst for transformation of alkanes to alcohols, ketones, carboxylic acids, and/or nitroalkanes under mild oxidation conditions [64]. Koguchi et al. [64] used NHPl-Co(OAc)j-02 system for the oxidation of alcohols in ionic liquids. They found that NHPI is separated easily from ionic liquid... 

Electrochemical anodic oxidation of amides and W-alkyllactams can be carried out with A(-hydroxy-phthalimide as mediator. Oxidation takes place predominantly at the endocyclic caibon a to the nitrogen. The susceptibility of five-membered rings to oxidation is much higher than that of six-membered rings. 

Finally, as examples of similar types of reactions, photolytic treatment of O-acyl ester (D) of benzophenone oxime, A-acyloxy-phthalimide (E), and O-acyl ester (F) of A-hydroxy-2-pyridone with a mercury lamp generates the corresponding alkyl radicals via decarboxylation. However, these reactions can be used only for the alkylation of aromatics (solvents such as benzene) and reduction [86-89], so their synthetic utility is extremely limited. 

HYDROXYMETHYLPHTHALIMIDE see HMPlOO N-(HYDROXYMETHYL)PHTHALIMIDE see HMPlOO 17-HYDROXY-6-METHYLPREGNA-4,6-DIENE-3,20-DIONE ACETATE see VTFOOO 17-HYDROXY-6-a-METHYLPREGN-4-ENE-3,20-DIONE ACETATE see MCAOOO 17-a-HYDROXY-6-a-METHYLPREGN-4-ENE-3,20-DIONE ACETATE see MCAOOO 17-a-HYDROXY-6-a-METHYLPROGESTERONE ACETATE see MCAOOO... 

N-Acetoxyphthalimide (2). The reagent is prepared by reaction of sodium N-hydroxy-phthalimide (which see) with acetyl chloride. It is recommended specifically - for N-acetylation of muramlc acid (1), since acetylation with acetic anhydride and pyridine gives products of intramolecular cyclization (lactams). Osawa and Jeanloz treated a solution of (1) in methanol at 0° with 2 equivalents of the reagent and 1 equivalent of triethylamine and let the mixture stand at room temperature for 20 hrs. 

Oxidation of phe dihydroxybiaryls in the a-Hydroxy-y-butyr combined in an oxidatr phthalimide, Co(acac) . i... 

Another method for the conversion of an alkene into an allylic alcohol, but with a shift in the position of the double bond, proceeds from the corresponding p-hydroxyselenide. The p-hydroxyselenide can be obtained from the epoxide by reaction with phenylselenide anion or directly from the alkene by addition of phenylselenenic acid, phenylselenenyl chloride in aqueous MeCN, or by acid-catalysed reaction with A-phenylseleno-phthalimide. The hydroxyselenide does not need to be isolated, but can be oxidized directly with tert-BuOOH to the unstable selenoxide, which spontaneously eliminates phenylselenenic acid to form the E-allylic alcohol. For example, 4-octene gave 5-octen -ol (6.15). Elimination takes place away from the hydroxy group to give the allylic alcohol no more than traces... 

Several other reactions involving C-N bond formation have been reported. A Ritter-type reaction of alkylbenzenes with nitriles has been achieved. Thus, the treatment of ethylbenzene with CAN in the presence of a catal3dic amount of N-hydroxy-phthalimide (NHPI) in EtCN produces the corresponding amide in good selectivity (eq 23). The reaction is also applicable to a number of unactivated hydrocarbons. As a comparison, the photolysis of admantane with CAN gives a mixture of products. In another case, the oxidation of monoterpenes such as pinene with CAN in acetonitrile affords the corresponding bisamides in good yields (eq 24). ... 

Two different N-protected hydroxylamines have been used to accomplish the synthesis of these novel hydroxylamine-functionalized resins. fV-Hydroxy-phthalimide has been employed in two ways first, as a nucleophile to splace either a resin-bound chloride ion (30) or a resin-bound mesylate ion (31) Figure 8a) and second, to generate the active phosphonium species required to perform a Mitsunobu reaction on a hydroxyl-functionalized resin (32) (Figure 8b). In both cases, the resin-bound iV-hydroxyphthalimide ester that is generated is subsequently treated with hydrazine to afford resin-bound hydroxylamine. 

Fig. 2.14 Examples of functionalized polymer films bearing reactive groups for covalent anchoring of biomolecules. (A) amines (PANI), (B) carboxyls (PTh), (C) N-hydroxysuccinimide esters (PPy), (D) pentafluorophenyl esters (PPy), (E) N-hydroxy-phthalimide esters (PPy), (F) aldehydes (PTh) (Reprinted from Ref. [144] with the permission of Royal Society of Chemistry)...

Various nucleophilic attacks at C(3) and C(4) of -lactams have been employed to introduce desired functionalities. Nucleophilic displacement of a halogen at C(3) by nucleophiles, for example, potassium phthalimide, has been performed (93JCS(Pl)2357). The a-azidation of l-hydroxy-2-azetidi-nones, for example (37), with arenesulfonyl azides in the presence of triethylamine affords 3-azido-2-azetidinones (38) via Otosylation and SN2 -type of displacement of the tosyloxy group (92JA2741, 93JA548, 93BMC2429). 

Very few compounds of this type are known, and none bear a 2-hydroxy group. The phthalimides (322), on cathodic reduction in anhydrous aceto-... 

The alkylation products are synthetically useful because simple subsequent transformations furnishes precursors of important natural products as illustrated in Scheme 8E.23. Simple oxidative cleavage of allylic phthalimide 45 generates protected (5)-2-aminopimelic acid, whose dipeptide derivatives have shown antibiotic activity. The esterification via deracemization protocol is not limited to the use of bulky pivalic acid. The alkylation with sterically less hindered propionic acid also occurs with high enantioselectivity to give allylic ester 116, which has been utilized as an intermediate towards the antitumor agent phyllanthocin and the insect sex excitant periplanone. Dihydroxylation of the enantiopure allylic sulfone gives diol 117 with complete diastereoselectivity. Upon further transformation, the structurally versatile y-hydroxy-a,(f-un-saturated sulfone 118 is readily obtained enantiomerically pure. 

The formation of dibenzopyrrolizines (51) on irradiation of N-(2-alkylphenyl)phthalimides (50) with a high-pressure mercury lamp was reported. Phthalimides containing electron-donating groups resisted cyclization. Hydroxy compounds 51 were dehydrated to dibenzopyrrolizinones by treatment with acids.38... 

The substitution pattern of TfOH-mediated electrophilic aminomethylation of psoralens (furo-coumarins) by V-(hydroxymethyl)phthalimide has been elucidated <85JHC73>. Multiple phthal-imidoylated adducts were obtained when a B-ring hydroxy or methoxy activating group was present, and these resisted simple cleavage with NH2NH2. However, this two-step procedure to aminomethyl group introduction worked well when the psoralens contained only methyl substituents. 

---