Baylis−Hillman-Type Carbon−Carbon Bond Formation of Alkenylphosphonates by the Action of Lithium Diisopropylamide

α-Phosphonovinyl Carbanions in Organic Synthesis

“…Furthermore, the LDA 18 or DABCO 19 -mediated Baylis-Hillman type reaction of vinylphosphonates with aldehydes or ketones also serves as a useful tool for an alternative preparation of 2-phosphonoallyl alcohols, which are intermediate reagents in allene synthesis.…”

Asymmetric Addition of Chiral 1,3,2‐Benzoxazaphosphinine 2‐Oxides to Aldehydes: Diastereoselective Synthesis of α‐Substituted β‐Hydroxyphosphonic Acids

“…[7] α-Substituted β-hydroxyphosphonates have been synthesized by the addition of phosphorylated anions to carbonyl groups [5] or by Baylis-Hillman reaction of vinylphosphonates. [8,9] The stereoselectivity of these processes is usually low and there are a few methods that lead to the creation of two new chiral centers with good diastereoselectivity. [10] Recently, we [11] and others [12] reported on the stereoselective synthesis of α-alkylphosphonic acids using chiral perhydro-1,3,2-benzoxazaphosphinine 2-oxides derived from (-)-8-aminomenthol with good diastereocontrol and now we summarize our results on the preparation of enantiopure α-alkyl-substituted β-hydroxyphosphonic acids using the same chiral template.…”

Amine and Titanium (IV) Chloride, Boron (III) Chloride or Zirconium (IV) Chloride-Promoted Baylis-Hillman Reactions

“…To overcome these shortcomings many variations have been devised, such as the use of Lewis acids or various other additives to activate the carbonyl electrophiles [ 6 , 7 , 8 , 9 , 10 ]. Among those Lewis acids examined, TiCl 4 has been successfully used to promote the Baylis-Hillman reaction in the presence of Lewis base catalysts [ 9 , 11 , 12 ]. During our own investigations of the Baylis-Hillman process we found that many amines are very effective Lewis bases in this interesting reaction and the reaction products differ considerably from those reported so far [ 13 ].…”