Abramov reaction phosphorus nucleophile-carbonyl

If a nucleophilic addition at a carbonyl or imine carbon occurs, the product is still a phosphinate (from a phosphonous ester) or a phosphine oxide (from a phosphinous ester), but the reaction is commonly referred to as an Abramov or Pudovik reaction. An example of the Pudovik reaction is shown below (equation 16). Addition of the phosphorus nucleophile to the /3-carbon atom of an a, /3-unsaturated substrate (Michael addition) is commonly referred to as a hydrophosphinylation reaction. ... 

The preparation of species such as a-hydroxyphosphonates has been alluded to only briefly here (see Section 3.5). We would note two direct approaches that are available for the preparation of these materials, both involving nucleophilic addition to carbonyl carbon. One of these is referred to as the Abramov reaction that involves the addition of a fully esterified trivalent phosphorus acid to a carbonyl carbon followed by a dealkylation of the phosphorus ester site. This preparation is quite inefficient when ordinary ester linkages are used, but the use of silyl esters overcomes most of these difficulties and allows facile isolation of the target compounds (equation 30). Note that reaction occurs preferentially at the carbonyl carbon and not by displacement of halogen at carbon. Addition occurs preferentially at carbonyl carbon compared to displacement at a carbon-halogen linkage, and provides product if removal of the ester linkage is facile. 

Addition of Phosphorus Nucleophiles to Carbonyl Compounds Additions of dialkyl H-phosphonates (the Pudovik reaction) or trialkyl phosphites (the Abramov reaction) to carbonyl compounds constitute a convenient route to a-hydroxyphosphonates (Scheme 47.7). 

This reaction was first reported by Pudovik in 1950. It is a base-promoted nucleophilic addition of organophosphorus anion to alkenes or alkynes and is generally known as the Pudovik reaction. Occasionally, it is also referred to as the Pudovik addition. In addition, since Abramov discovered a similar addition reaction of phosphorus compounds to carbonyl compounds at the same time, the addition of organophosphorus compounds to activated unsaturated systems (e.g., alkenes, alkynes, ketones, aldehydes,and... 

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