Direct Conversion of Benzylic and Allylic Alcohols to Phosphonates

Barney, Rocky J.; Richardson, Rebekah M.; Wiemer, David F.

doi:10.1021/jo200137k

Cited by 64 publications

(57 citation statements)

References 50 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The classical method for the transformation of the allylic alcohol into the corresponding phosphonate through the labile chloride intermediate followed by Arbuzov reaction with neat trimethyl phosphite and NaI provided the expected product 17 b although in low yield. Alternatively, the direct transformation induced by treatment of the alcohol with ZnI 2 and triethyl phosphite50 gave rise to phosphonate 17 a in good yield. The Sonogashira reaction with enyne 16 by using [Pd(PPh 3 ) 4 ] as the catalyst in the presence of CuI and Et 3 N afforded the coupled product 15 (56 %).…”

Section: Resultsmentioning

confidence: 99%

Total Synthesis of Enantiopure Pyrrhoxanthin: Alternative Methods for the Stereoselective Preparation of 4‐Alkylidenebutenolides

Vaz

Otero

Álvarez

et al. 2013

Chemistry A European J

View full text Add to dashboard Cite

A new stereocontrolled total synthesis of the configurationally labile C37 -norcarotenoid pyrrhoxanthin in enantiopure form has been completed. A highly stereoselective Horner-Wadsworth-Emmons (HWE) condensation of a C17-allylphosphonate and a C20-aldehyde was used as the last conjunctive step. Both a Sonogashira reaction to form the C17-phosphonate and the final HWE condensation proved to be compatible with the sensitive C7-C10 enyne E configuration. Regioselective (5-exo-dig) silver-promoted lactonization reactions of three alternative pent-2-en-4-ynoic acid precursors with increased complexity, including a fully functionalized C20-fragment, were explored for the preparation of the γ-alkylidenebutenolide fragment. This survey extends the existing methodologies for the preparation of oxygen-containing carotenoids (xanthophylls) and streamlines the synthesis of additional members of the C37-norcarotenoid butenolide family of natural products.

show abstract

Section: Resultsmentioning

confidence: 99%

Total Synthesis of Enantiopure Pyrrhoxanthin: Alternative Methods for the Stereoselective Preparation of 4‐Alkylidenebutenolides

Vaz

Otero

Álvarez

et al. 2013

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…Diethyl allyl phosphonate (DEAP) was synthesized using the Michaelis–Arbuzov reaction . MCO–DEAP polyol was synthesized using the thiol–ene reaction.…”

Section: Methodsmentioning

confidence: 99%

“…Diethyl allyl phosphonate (DEAP) was synthesized using the Michaelis-Arbuzov reaction. 18 MCO-DEAP polyol was synthesized using the thiol-ene reaction. For this, 50 g of MCO, 26 g of DEAP, and 3.5 g of 2-hydroxy-2-methylpropiophenone were added into a beaker.…”

Section: Synthesis Of Mco-diethyl Allyl Phosphonate Polyolmentioning

confidence: 99%

Castor‐oil derived nonhalogenated reactive flame‐retardant‐based polyurethane foams with significant reduced heat release rate

Bhoyate

Ionescu

Kahol

et al. 2018

J of Applied Polymer Sci

View full text Add to dashboard Cite

National Fire Protection Association encounters one structural fire every 66 s. Rigid polyurethane foam is one of the principal components used in constructional and household applications. In this work, a reactive flame retardant (FR) was synthesized using a facile one‐step thiol–ene reaction by reacting mercaptenized castor oil (MCO) and diethyl allyl phosphonate (DEAP). The obtained MCO–DEAP polyol was used for the preparation of polyurethanes having different weight percentages of phosphorus (P). Addition of FR polyol showed no adverse effect on the cellular structure of the foams and maintained the compressive strength. All the foams showed closed cell content greater than 95%. Horizontal burning test (HBT) was performed before and after the migration test to understand the stability of the FR within the foams. Foams showed no relative weight loss before and after the migration test and maintained equivalent results for HBT. For 1.5 wt % P foams, low extinguishing time of 3 s and weight loss of 4% was observed. The cone calorimeter test showed a reduction in the peak heat release rate from 313 to 158 kW m−3, the total heat release from 18 to 8 MJ m−2, and O2 consumption from 12 to 6 g. Our results suggest that MCO–DEAP polyol could act as an essential FR for rigid PU foam ensuring fire safety. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47276.

show abstract

“…Recently, an efficient protocol for the conversion of common allyl and benzyl alcohols into the corresponding phosphonates through their treatment with triethyl phosphite and ZnI 2 , was described [16]. Similarly, Das and co-workers [17] have directly converted acyclic Morita–Baylis–Hillman (MBH) alcohols into the corresponding allylphosphonates upon their treatment with trialkyl phosphite in the presence of FeCl 3 (Scheme 1, reaction 2).…”

Section: Introductionmentioning

confidence: 99%

First DMAP-mediated direct conversion of Morita–Baylis–Hillman alcohols into γ-ketoallylphosphonates: Synthesis of γ-aminoallylphosphonates

Ayadi¹,

Elleuch²,

Vrancken³

et al. 2016

Beilstein J. Org. Chem.

View full text Add to dashboard Cite

An efficient synthesis of a series of γ-ketoallylphosphonates through a direct conversion of both primary and secondary Morita–Baylis–Hillman (MBH) alcohols by trialkyl phosphites with or without DMAP, used as additive, and under solvent-free conditions, is described herein for the first time. Subsequently, a highly regioselective Luche reduction of the primary phosphonate 2a (R = H) gave the corresponding γ-hydroxyallylphosphonate 5 that further reacted with tosylamines in the presence of diiodine (15 mol %) as a catalyst, affording the corresponding SN2-type products 6a–d in 63 to 70% isolated yields. Alternatively, the alcohol 5 produced the corresponding acetate 7 which, mediated by Ce(III), was successfully converted into the corresponding γ-aminoallylphosphonates 8a–d.

show abstract

Direct Conversion of Benzylic and Allylic Alcohols to Phosphonates

Cited by 64 publications

References 50 publications

Total Synthesis of Enantiopure Pyrrhoxanthin: Alternative Methods for the Stereoselective Preparation of 4‐Alkylidenebutenolides

Total Synthesis of Enantiopure Pyrrhoxanthin: Alternative Methods for the Stereoselective Preparation of 4‐Alkylidenebutenolides

Castor‐oil derived nonhalogenated reactive flame‐retardant‐based polyurethane foams with significant reduced heat release rate

First DMAP-mediated direct conversion of Morita–Baylis–Hillman alcohols into γ-ketoallylphosphonates: Synthesis of γ-aminoallylphosphonates

Contact Info

Product

Resources

About