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Unequivocal experimental evidence for a unified lithium salt-free Wittig reaction mechanism for all phosphonium ylide types: reactions with β-heteroatom-substituted aldehydes are consistently selective for cis-oxaphosphetane-derived products
Byrne, Peter A.; Gilheany, Declan G.
The true course of the lithium salt-free Wittig reaction has long been a contentious issue in organic chemistry. Herein we report an experimental effect that is common to the Wittig reactions of all of the three major phosphonium ylide classes (non-stabilized, semi-stabilized, and stabilized): there is consistently increased selectivity for cis-oxaphosphetane and its derived products (Z-alkene and erythro-B-hydroxyphosphonium salt) in reactions involving aldehydes bearing heteroatom substituents in the B-position. The effect operates with both benzaldehydes and aliphatic aldehydes and is shown not to operate in the absence of the heteroatom substituent on the aldehyde. The discovery of an effect that is common to reactions of all ylide types strongly argues for the operation of a common mechanism in all Li salt-free Wittig reactions. In addition, the results are shown to be most easily explained by the [2+2] cycloaddition mechanism proposed by Vedejs and co-workers as supplemented by Aggarwal, Harvey, and co-workers, thus providing strong confirmatory evidence in support of that mechanism. Notably, a cooperative effect of ortho-substituents in the case of semi-stabilized ylides is confirmed and is accommodated by the cycloaddition mechanism. The effect is also shown to operate in reactions of triphenylphosphine-derived ylides and has previously been observed for reactions under aqueous conditions, thus for the first time providing evidence that kinetic control is in operation in both of these cases.
Keyword(s): Cycloaddition mechanism; Triphenylphosphine-derived ylides; Kinetic diasteros electivity; Stereochemical drift
Publication Date:
2012
Type: Journal article
Peer-Reviewed: Yes
Language(s): English
Institution: University College Dublin
Publisher(s): American Chemical Society
Related Link(s): http://dx.doi.org/10.1021/ja300943z
First Indexed: 2013-11-16 05:17:20 Last Updated: 2018-04-14 06:23:55