Acyl Phosphonates Research Articles

Self-condensation reactions of acyl phosphonates: synthesis of tertiary $O$-protected $\alpha $-hydroxyphosphonates

The self-condensation reaction of benzoyl dialkyl phosphonates was developed using cyanide ion as catalyst, affording versatile tertiary O-protected a-hydroxy phosphonates in moderate yield.

ChemInform Abstract: Diametric Stereocontrol in Dynamic Catalytic Reduction of Racemic Acyl Phosphonates: Divergence from α‐Keto Ester Congeners.

AbstractAn unexpected reversal in facial selectivity is observed in the Ru(II)‐catalyzed asymmetric transfer hydrogenation of acyl phosphonates in comparison to their previously studied structural mimics, α‐keto esters.

Ruthenium-Catalyzed Dynamic Kinetic Resolution of Acyl Phosphonates

Key words ruthenium - acyl phosphonates - transfer hydrogenation - dynamic kinetic resolution - α-hydroxy phosphonic acid

Diametric stereocontrol in dynamic catalytic reduction of racemic acyl phosphonates: divergence from α-keto ester congeners.

An unexpected dichotomy was observed in the Ru-catalyzed asymmetric transfer hydrogenation of acyl phosphonates: reduction proceeded from the opposite face relative to that observed in the analogous reduction of α-keto esters. The first highly selective catalytic hydrogenation of acyl phosphonates was utilized in the dynamic kinetic resolution of α-aryl acyl phosphonates, providing β-stereogenic α-hydroxy phosphonic acid derivatives.

Diametric Stereocontrol in Dynamic Catalytic Reduction of Racemic Acyl Phosphonates: Divergence from α-Keto Ester Congeners

Diametric Stereocontrol in Dynamic Catalytic Reduction of Racemic Acyl Phosphonates: Divergence from α-Keto Ester Congeners

ChemInform Abstract: Transition‐Metal‐Catalyzed Cyclization of Alkynals via Oxametallacycle Intermediates

AbstractReview: Ni, Rh, Ru, Ti; 82 refs.

A Practical Synthesis of Alendronate Sodium through Counterattack Reaction

An efficient synthesis of alendronate sodium, an osteoporosis drug, has been developed through ‘counterattack reaction’ involving treatment of the respective acyl phosphonate with (MeO)₃P and TMSBr followed by deblocking with aqueous HCl.

Transition‐Metal‐Catalyzed Cyclization of Alkynals via Oxametallacycle Intermediates

AbstractThe transition‐metal‐catalyzed cyclization of alkynals viaoxametallacycle intermediates is a useful method for thestereoselective synthesis of cyclic allylic alcohol derivatives. The reductive cyclization reactions are catalyzed by titanium and nickel complexes using organosilanes, organoboranes, and organozincs as reducing agents. The alkylative, arylative, and alkenylative cyclization reactions are catalyzed by nickel complexes using organozincs and alkenylzirconiums. On the other hand, the recently developed rhodium‐catalyzed reductive cyclization reactions of alkynals allow using dihydrogen as a reducing agent without the use of organometalloid and organometallic reagents. Furthermore, very recently, the rhodium‐catalyzed acylative cyclization reactions of alkynals were accomplished by using aldehydes and acyl phosphonates as acylating reagents. Importantly, the use of the rhodium catalysts realized the enantioselective cyclization reactions of alkynals with excellent levels of enantioselection.

ChemInform Abstract: Rhodium‐Catalyzed Enantioselective Cyclizations of γ‐Alkynylaldehydes with Acyl Phosphonates: Ligand‐ and Substituent‐Controlled C—P or C—H Bond Cleavage.

ChemInformVolume 42, Issue 37 Heterocyclic Compounds ChemInform Abstract: Rhodium-Catalyzed Enantioselective Cyclizations of γ-Alkynylaldehydes with Acyl Phosphonates: Ligand- and Substituent-Controlled C—P or C—H Bond Cleavage. Kengo Masuda, Kengo Masuda Dep. Appl. Chem., Grad. Sch. Eng., Tokyo Univ. Agric. Technol., Koganei, Tokyo 184, JapanSearch for more papers by this authorNorifumi Sakiyama, Norifumi Sakiyama Dep. Appl. Chem., Grad. Sch. Eng., Tokyo Univ. Agric. Technol., Koganei, Tokyo 184, JapanSearch for more papers by this authorRie Tanaka, Rie Tanaka Dep. Appl. Chem., Grad. Sch. Eng., Tokyo Univ. Agric. Technol., Koganei, Tokyo 184, JapanSearch for more papers by this authorKeiichi Noguchi, Keiichi Noguchi Dep. Appl. Chem., Grad. Sch. Eng., Tokyo Univ. Agric. Technol., Koganei, Tokyo 184, JapanSearch for more papers by this authorKen Tanaka, Ken Tanaka Dep. Appl. Chem., Grad. Sch. Eng., Tokyo Univ. Agric. Technol., Koganei, Tokyo 184, JapanSearch for more papers by this author Kengo Masuda, Kengo Masuda Dep. Appl. Chem., Grad. Sch. Eng., Tokyo Univ. Agric. Technol., Koganei, Tokyo 184, JapanSearch for more papers by this authorNorifumi Sakiyama, Norifumi Sakiyama Dep. Appl. Chem., Grad. Sch. Eng., Tokyo Univ. Agric. Technol., Koganei, Tokyo 184, JapanSearch for more papers by this authorRie Tanaka, Rie Tanaka Dep. Appl. Chem., Grad. Sch. Eng., Tokyo Univ. Agric. Technol., Koganei, Tokyo 184, JapanSearch for more papers by this authorKeiichi Noguchi, Keiichi Noguchi Dep. Appl. Chem., Grad. Sch. Eng., Tokyo Univ. Agric. Technol., Koganei, Tokyo 184, JapanSearch for more papers by this authorKen Tanaka, Ken Tanaka Dep. Appl. Chem., Grad. Sch. Eng., Tokyo Univ. Agric. Technol., Koganei, Tokyo 184, JapanSearch for more papers by this author First published: 18 August 2011 https://doi.org/10.1002/chin.201137107Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume42, Issue37September 13, 2011 RelatedInformation

ChemInform Abstract: Hetero Diels—Alder Reactions of Acyl Phosphonates: Synthesis of Glycosyl Type Phosphonates.

AbstractThe hetero Diels—Alder reaction of acyl phosphonates with activated dienes is presented.

Rhodium-Catalyzed Enantioselective Cyclizations of γ-Alkynylaldehydes with Acyl Phosphonates: Ligand- and Substituent-Controlled C–P or C–H Bond Cleavage

It has been established that a cationic rhodium(I)/(R)-H(8)-BINAP or (R)-Segphos complex catalyzes two modes of enantioselective cyclizations of γ-alkynylaldehydes with acyl phosphonates via C-P or C-H bond cleavage. The ligands of the Rh(I) complexes and the substitutents of both γ-alkynylaldehydes and acyl phosphonates control these two different pathways.

Indium triflate-catalyzed coupling of indoles with acyl phosphonates: synthesis of bis(indolyl)methane phosphonates

The coupling reaction of N-methylindole with alkyl and aryl phosphonate is described. The reaction works in the presence of 10 mol % of indium triflate and furnished bis(indolyl)methane phosphonates in good yield and high selectivity.

Reactions of acyl phosphonates with organoaluminum reagents: a new method for the synthesis of secondary and tertiary α-hydroxy phosphonates

The reactions of organoaluminum reagents (trimethylaluminum, triethylaluminum, etc.) with aryl and alkyl acyl phosphonates, which lead to the formation of α-hydroxy phosphonates in moderate to good yields, are reported. This method provides easy access to secondary and tertiary α-hydroxy phosphonates depending on the reaction conditions. The reactions of triethylaluminum with a series of acyl phosphonates at 0 °C gave the secondary α-hydroxy phosphonates, while at −100 °C they afford the tertiary α-hydroxy phosphonates.

Hetero Diels–Alder reactions of acyl phosphonates: synthesis of glycosyl type phosphonates

We have prepared glycosyl type phosphonates via hetero Diels–Alder (HDA) reactions of acyl phosphonates with electron rich dienes. HDA reactions of acyl phosphonates with Danishefsky’s diene required thermal activation to yield the desired dihydropyranones in good yield (70–91%). The reactions with Brassard’s diene involved Lewis acid promotion to yield the corresponding lactones, though in moderate yield (33–69%).

ChemInform Abstract: Room‐Temperature Alternative to the Arbuzov Reaction: The Reductive Deoxygenation of Acyl Phosphonates.

AbstractA one‐pot multistep procedure to prepare alkyl phosphonates from the commercially available acid chlorides or from acid chlorides, generated in situ from the corresponding carboxylic acids with oxalyl chloride.

ChemInform Abstract: Enantioselective Friedel—Crafts Alkylation Reaction of Indoles with α,β‐Unsaturated Acyl Phosphonates Catalyzed by Chiral Phosphoric Acid.

AbstractA variety of indoles (I) undergo enantioselective Friedel—Crafts alkylation with α,β‐unsaturated acyl phosphonates (II) and (V) in the presence of a BINOL‐derived phosphoric acid.

ChemInform Abstract: An Efficient Synthesis of Some Substituted Vinylic Chloroformates: Reaction Scope and Limitations.

2,2-Dichlorovinyl chloroformate is isolated in 50% distilled yield when chloral is treated with phosgene and zinc dust in 2:1 methyl acetate/ether. The reaction has been extended to other α-chloro and α-bromo aldehydes and ketones in which both other α-positions are occupied by either halo and/or alkyl groups. The reaction fails with hydrogen in an α-position. Similar treatment of α-halo esters gives only the C-acylated products expected from a Reformatsky type reaction, while ketenes are the well-known products from α-halo acid chlorides. However, acyl cyanides and acyl phosphonates, with leaving groups intermediate between fluoride and alkoxide, are converted to chloroformates; e.g., Me 2 C=C(CN)OC(=O)Cl in 67% yield and Me 2 C=C[P(O)(OMe) 2 ]OC(=O)Cl in 83% yield. Carbonates and urethans from these chloroformates are of interest as monomers, pesticides, and chemical intermediates

Room-Temperature Alternative to the Arbuzov Reaction: The Reductive Deoxygenation of Acyl Phosphonates

The reductive deoxygenation of acyl phosphonates using a Wolff-Kishner-like sequence is described. This transformation allows direct access to alkyl phosphonates from acyl phosphonates at room temperature. The method can be combined with acyl phosphonate synthesis into a one pot, four-step procedure for the conversion of carboxylic acids into alkyl phosphonates. The methodology works well for a variety of aliphatic acids and shows a functional group tolerance similar to that of other hydrazone-forming reactions.

ChemInform Abstract: The Preparation of Acyl Phosphonates by the Heterogeneous Oxidation of 1-Hydroxy Phosphonates.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform Abstract: Surface-Mediated Solid-Phase Reactions: The Preparation of Acyl Phosphonates by Oxidation of 1-Hydroxyphosphonates on the Solid Surface.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.