Remote Stereocontrol in the Synthesis of Acyclic 1,4-Diols and 1,4-Aminoalcohols from 2-Sulfinyl Dienes

Abstract

The highly diastereoselective conjugate addition of alcohols and amines (RXH) to enantiopure 2-sulfinyl dienes renders transient allylic sulfoxides which undergo sulfoxide-sulfenate rearrangement and sulfenate cleavage providing 2-ene-1,4-diols and 2-ene-1,4-aminoalcohols with up to 99:1 dr. The method allows for the generation of two stereocenters in a single synthetic operation with remote chirality transfer of one center into the other.

Polyoxygenated Cyclohexenes and Their Chlorinated Derivatives from the Leaves of Uvaria cherrevensis

“…The absolute configuration of 12 was assigned via an appraisal of the sign of its specific rotation {[α] 25 D −3 (c 0.1, CHCl 3 )} with the related synthesized compound (+)-(2S,3E,5E)-nona-3,5-diene-1,2-diol {[α] 25 D +10 (c 0.5, CHCl 3 )}. 20 Therefore, cherrevenol L ( 12) was tentatively assigned the R configuration. However, an insufficient amount of 12 was available for Mosher ester analysis.…”

Bond-Forming and -Breaking Reactions at Sulfur(IV): Sulfoxides, Sulfonium Salts, Sulfur Ylides, and Sulfinate Salts

“…De la Pradilla and co-workers have furthermore exploited the stereoretentive nature of [2,3]-sigmatropic rearrangements for the construction of allylic stereocenters following conjugate addition to enantiopure vinyl sulfoxide derivatives (Scheme 38). 138,139 A related approach (not shown) was chosen by Zard and co-workers for the synthesis of α-keto vinyl carbinols. 140 At the beginning of this decade, the groups of Poli and Norrby investigated the synthesis of diaryl sulfoxides from allyl aryl sulfoxides (Scheme 39).…”

Diastereodivergent Synthesis of 2-Ene-1,4-hydroxy Sulfides from 2-Sulfinyl Dienes via Tandem Sulfa-Michael/Sulfoxide-Sulfenate Rearrangement

“…Within this field, thiol or thiolate additions to substituted alkenyl sulfoxides are relatively rare and unselective in some cases . In recent years we have been involved in the application of readily available 1-sulfinyl dienes A and 2-sulfinyl dienes C (X = O, NTs, NR′; Y = O, NR′; Scheme ) in stereoselective synthesis, including the conjugate addition of amines and alkoxides (R 3 YH, RXH) to produce allylic sulfoxide intermediates that underwent a [2,3]-sigmatropic rearrangement, ultimately leading to 1,4-diol or 1,4-aminoalcohol derivatives B in a cascade process, with good yields and stereoselectivities . These results prompted us to examine the conjugate addition of thiolates to 2-sulfinyl dienes D , readily available from iodides or stannanes 1 (Scheme ), that could afford allylic sulfoxides E , and ultimately lead to allylic sulfides F .…”