Hanessian reaction

M. L. Wolffom and S. Hanessian, Reaction of free carbonyl sugar derivatives with organo-metallics reagents. II 6-Deoxy-L-idose and a branched-chain sugar, J. Org. Chem. 27 2107 (1962). 

An interesting synthesis of a methyl-branched anthracycline has been reported [58], The methyl-branched 3-amino-ribo derivative 93 was opened by Hullar-Hanessian reaction to 94, transformed into the exocyclic glycal 95, inverted at C-5 and reacted to the glycal precursor 96. Its treatment with the aglycone and p-toluenesulfonic acid gave the derivative 97. 

Cyclic benzylidene acetals have also been found to react with IN3 to provide ring-opened product via an azido-Hanessian reaction (Scheme 8.19)." ... 

The synthesis of 11-oxaprostaglandlns from o-glucose uses the typical reactions of gl cofuranose diacetonide outlined on p. 267. Reduction of the hemiacetal group is achieved a thioacetal. The carbon chains are introduced by Wittig reactions on the aldehyde grou] which are liberated by periodate oxidation and laaone reduction (S. Hanessian, 1979 G Lourens, 1975). 

Hanessian reported the synthesis of enantiomerically pure or highly enriched allylglycine and its chain-substituted analogs from the reaction of the sultam derivatives of O-benzyl glyoxylic acid oxime with ally he bromides in the presence of zinc powder in aqueous ammonium chloride (Eq. 11.41).72 Brown noticed the critical importance of water in the asymmetric allylboration of /V-trimethylsilyIbcnzaldimines with B-allyldiisopinocampheylborane.73 The reaction required one equivalent of water to proceed (Eq. 11.42). 

Bimolecular, nucleophilic-displacement reactions of sugar sulfonates have been reviewed in this Series.58,59 The value of these reactions in the preparation of deoxyhalo sugars has been emphasized by Hanessian.92... 

E. D. Binkley and R. W. Binkley, SN2-Type Halogenation and Azidation Reactions with Carbohydrate Triflates, ed. S. Hanessian, Marcel Dekker, New York, 1997. 

Hanessian described the facile addition of cyclic and acyclic nitroalkanes to cyclic a,P-unsaturated ketones using L-proline 58 as the catalyst (3-7 mol%) in the presence of 2,5-dimethylpiperazine [100], The reactions proceeded efficiently at room temperature and consistently provided adduct 59 with increased levels of enantioselectivity when compared with the rubidium prolinate method disclosed by Yamaguchi [29] (Scheme 24). The presence of trace amounts of water in the reaction was found to be essential, suggesting a hydrolytic step is involved in the catalytic... 

The reactivity of the methoxyethy1idene derivatives with nucleophiles other than water has been examined. It has been already found (13) that they may be readily opened by halogenating reagents ( N -b romo succ i n i-mide for instance) to give a or 3-ha 1 oacetates (respectively from five- or six-membered-ring orthoesters), and this reaction may be compare with the familiar Hanessian procedure for conversion of henzylidene acetals iiito bro-mo-deoXybenzoates (68). ... 

Hanessian s group investigated the addition reactions of oximes using bis(oxazo-line) ligand As shown in Figure 9.55b, reaction of the a-oximino ester... 

Hanessian and Compain have also reported a Lewis acid-promoted inverse electron demand hetero-Diels-Alder reaction between dihydrofurans and dihydropyrans with a-keto-/3,7-unsaturated phosphonates to give stmcturally related products <2002T6521>. High-pressure OTr/o-selective hetero-Diels-Alder reactions between a,/3-unsaturated aldehydes and enol ethers in the presence of lanthanide catalysts have also been reported and give 3,4-dihydro-27/-pyrans. Examples include the use of cyclic enol ethers to give 2,3,4,4a,5,8a-hexahydro-277,577-pyrano[2,3-. ]pyrans <1995T8383>. 

C-3 (or C-4) from a 1,3-dioxolane actually, this reaction (see Section HI, 14) was observed for 2,2-disubstituted 1,3-dioxolanes, and it may be assumed that, if there is any competition between removal of a proton from C-2 and from C-3 (or C-4), the rate of the first reaction is far greater than that of the second. The possibility of dioxolanylium ions reacting with nucleophilic reagents was first demonstrated by Hanes-sian and Staub,152 and the scope of these reactions was independently investigated by Pedersen and coworkers.153-157 Hanessian and Staub152 treated methyl 5-0-benzoyl-2,3-0-benzylidene-j3-D-ribofuranoside (125) with triphenylmethyl fluoroborate in acetonitrile, and obtained, after hydrolysis, a 1 1 mixture of the two benzoates 127 and 128 (yield 83%), probably through the benzoxonium ion 126. The same reaction... 

During the past decade, almost all of the remaining branched sugars were synthesized, mainly by the application of new techniques, and the structure of several sugars was finally determined by their synthesis. In addition, better understanding as to the selectivities of reactions used was attained from the data accumulated, and this is important for stereospecific synthesis. The present article concentrates on these advances. Although most of the reactions for the introduction of carbon branching are also applicable for chain extension, the latter will be excluded here. Some of them were described in an article by Hanessian and Pernet.94... 

S. Hanessian and N. R. Plessas, Reactions of carbohydrates with (halomethylene)dimethyl-iminium halides and related reagents. Synthesis of some chlorodeoxy sugars, J. Org. Chem. 34 2163 (1969). 

S. Hanessian and P. Lavallee, Selective substitution reactions of a,a-trehalose Preparation of 6-monofunctional derivatives, Carbohydr. Res. 38 303 (1973). 

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