The intraand intermolecular condensation of alcohols with bis-sulfone methylenes, i.e., dehydrative alkylation, using DEAD and PhgP proceeds stereospecifically at room temperature under essentially neutral conditions affording good to excellent yields of alkylation/ annulation products.The classic Mitsunobu condensation2 of an alcohol with a carboxylic acid, mediated by dialkyl azodicarboxylate/ triphenylphosphine, involves the in situ generation of a highly reactive alkoxyphosphonium intermediate3 which undergoes nucleophilic displacement under mild, nearly neutral conditions with virtually complete inversion of configuration at the electrophilic site (eq 1). Numerous PPh3 ro2cn=nco2r HX OPPh3 V ' y (eq 1) X = RC02", RCOS", RN", ArO'JsO; R3S¡0" I", Br", Cl", F, CNT modifications4 of this protocol have extended its utility to other types of nucleophiles, inter alia, thiolacetate, halides, silanols, tosylate, phthalimide, and heterocycles. Our recent observation5 that DEAD/PhsP complex converts 7-nitroalkanols to -nitrocyclopropanes in good to excellent yields represents a rare example of participation by a carbon-centered nucleophile.6 However, all efforts to exploit the latter dehydrative alkylation of nitro paraffins to form larger rings or for intermolecular condensations failed and, thus, prompted us to evaluate other functionalities.7 Herein, we report that bis-sulfones are particularly effective for a wide variety of dehydrative alkylations/annulations8 as summarized in Table I. Cyclizations affording both small-(entries 1 and 2) and medium-sized rings (entry 3) were achieved with equal ease. Likewise, intermolecular alkylative dehydrations proceeded smoothly (entry 4) and, when applied to diols in the presence of excess reagent, provided