Asymmetric Alkylation of Nitroalkanes

✍ Scribed by Barry M. Trost; Jean-Philippe Surivet

• Publisher: John Wiley and Sons
• Year: 2000
• Tongue: English
• Weight: 118 KB
• Volume: 39
• Category: Article
• ISSN: 0044-8249
• DOI: 10.1002/1521-3773(20000901)39:17<3122::aid-anie3122>3.0.co;2-8

✦ Synopsis

The utility of nitro compounds as synthetic intermediates stems from the versatility of the reactivity of the nitro group. [1] One feature arises from the ease of formation of nitronate anions; however, their low reactivity generally limits the reactions they undergo to carbonyl and conjugate addition. [2] Alkylations do not normally proceed well. On the other hand, Pd-catalyzed allylic alkylations have had some success. [3] This success stimulates the search for an asymmetric allylic alkylation (AAA) which has had good results in only one case (the 1,3-diphenylallyl system) and when nitromethane was used as solvent. [4] We here report that the Pd-catalyzed AAA reaction [5] of nitroalkanes with cyclic allyl esters can proceed in high yields and enantioselectivities and provide a short asymmetric synthesis of a carbanucleoside.

Our initial studies focused on desymmetrization of meso diesters [Eq. ( 1)]. [6] Our earlier results suggested the diben-

[1] a) G.