Dedicated to Professor Andrew E. Greene on occasion of his retirementDuring the last decade, chemists have devoted much effort to the development of new asymmetric methodologies to build complex scaffolds in a highly enantioselective fashion.[1] Among the strategies employed, organocatalysis [2] has received widespread attention due to its unique properties such as metal-free environment, easy predictability of stereoselectivity, use of inexpensive catalysts, and simplicity of reaction conditions.Since the work on proline catalysis by List, Lerner, and Barbas III in 2000 [3] and that on iminium catalysis by MacMillan soon after, [4] organocatalysis has grown exponentially both by improving catalysts and by the discovery of new reactions. However, there are still a number of challenges and issues that lie ahead. One notable challenge is the use of "naked" methyl or alkyl synthons as suitable nucleophiles. The catalytic enantioselective conjugate addition of nonfunctionalized hydrocarbon fragments to a,b-unsaturated aldehydes is an unsolved problem in organic synthesis. Whereas in the past few years major breakthroughs have been realized in the metal-catalyzed enantioselective conjugate addition of Grignard reagents [5] and of other organometallic reagents [6] to a,b-unsaturated ketones, esters, or amides, only recently Bräse and co-workers reported on the asymmetric conjugate addition of diethylzinc to cinnamaldehyde, by using N,O-planar chiral [2.2]paracyclophane-derived ligands. [7] In the field of organocatalysis there are several carbon nucleophiles that can be used to form C À C bonds with unsaturated aldehydes. For example, Jorgensen and co-workers developed the addition of malonate to unsaturated aldehydes in excellent yields and enantioselectivities.[8] Soon after, several research groups developed similar routes to furnish a wide range of interesting scaffolds.[9] Among them, we can highlight useful asymmetric additions of ketoesters, [10] nitroalkanes, [11] N-nucleophiles, [12] S-nucleophiles, and O-nucleophiles [13] to unsaturated aldehydes. In spite of the fact that the addition of new functionalities in a molecule can be advantageous, the removal of these functional groups can be difficult and sometimes demands a protection-deprotection approach to render the desired "naked" product.To circumvent these disadvantages, we aimed to develop an easy method to add "naked" methyl or alkyl chains to unsaturated aldehydes. Bis(phenylsulfonyl)methane has been extensively used in organic chemistry. For example, in 1997 Trost and co-workers used bis(phenylsulfonyl)methane as a nucleophile in the palladium-catalyzed addition to alkenyl epoxides.[14] A recent application of this compound is its use as a fluoromethyl anion equivalent: bis(phenylsulfonyl)methane is easily fluorinated by treatment with NaH and Selectfluor, which furnishes fluorobis(phenylsulfonyl)-methane that can be used as a nucleophile in a broad range of reactions.[15] However, there are few examples of the use of bis(phenylsulfonyl)methane deriva...