Phosphorus‐Carbon Bond Formation: Palladium‐Catalyzed Cross‐Coupling of <i>H</i>‐Phosphinates and Other P(O)H‐Containing Compounds

Berger, Olivier; Petit, Christelle; Deal, Eric L.; Montchamp, Jean‐Luc

doi:10.1002/adsc.201300069

Cited by 133 publications

(57 citation statements)

References 136 publications

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“…Furthermore, although reducing the amount of mesitylene reduced the yield slightly, the same product could be obtained in 72 or 70 % yield using only 2 or 1 equiv of MesH, respectively. We previously synthesized a related compound through Pd‐catalyzed cross‐coupling of MesI in 61 % yield 15…”

Section: Methodsmentioning

confidence: 99%

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Manganese‐Mediated Intermolecular Arylation of H‐Phosphinates and Related Compounds

Berger

Montchamp

2014

Chemistry A European J

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The intermolecular radical functionalization of arenes with aryl and alkyl H-phosphinate esters, as well as diphenylphosphine oxide and H-phosphonate diesters, is described. The novel catalytic Mn(II) /excess Mn(IV) system is a convenient and inexpensive solution to directly convert Csp2 H into CP bonds. The reaction can be employed to functionalize P-stereogenic H-phosphinates since it is stereospecific. With monosubstituted aromatics, the selectivity for para-substitution increases in the order (RO)2 P(O)H

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Section: Methodsmentioning

confidence: 99%

“…This is perhaps due to a trade-off between steric hindrance and electronic effects. Finally, replacing excess MnO 2 with other oxidants (KMnO 4 , BaMnO 4 , and Mn(OAc) 2 ) was investigated but unsatisfactory (entries [14][15][16].…”

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confidence: 99%

Manganese‐Mediated Intermolecular Arylation of H‐Phosphinates and Related Compounds

Berger

Montchamp

2014

Chemistry A European J

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“…Addition of DIPEA and catalytic Pd/dppf in a mixture DMF/DME to the intermediates generated the corresponding cyclized derivatives 40a,b in yields up to 53% (Scheme 16) [18]. …”

Section: Reviewmentioning

confidence: 99%

Phosphinate-containing heterocycles: A mini-review

Berger¹,

Montchamp²

2014

Beilstein J. Org. Chem.

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SummaryThis review provides an overview of recent efforts towards the synthesis of phosphinate heterocycles R1R2P(O)(OR). Our laboratory and others’ have been involved in this field and as a result new P–C, P–N, and P–O containing heterocyclic motifs are now available through a variety of methods. While developing rapidly, this area is still in its infancy so that biological testing of the compounds has not yet been conducted and applications are rare. The growing availability of synthetic methods will undoubtedly change this situation in the near future.

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“…[3a,e, 6, 7] To the best of our knowledge, there is no previous report on the Tsuji-Trost reaction of allylic amines with phosphorus nucleophiles. Herein, we report efficient allylation reactions of hypophosphorous acid and Hphosphinic acids with primary allylic amines, which are more atom-economic relative to those with commonly used allylic electrophiles because ammonia is the sole byproduct.The Tsuji-Trost reaction has been successfully extended to the allylation of a few phosphorus nucleophiles for the synthesis of allylic-(H)-phosphinic acids and their derivatives.[8] Montchamp and co-workers reported that hypophosphorous acid, hypophosphite salts, [9] and H-phosphinic acids [10] could undergo palladium-catalyzed allylation with allylic alcohols, esters, and carbonates.[11] When allylic alcohols were used as the allylic electrophiles, they underwent Fischer-like esterification prior to palladium-catalyzed C À O bond cleavage. Inspired by these reports, together with our interest in exploring new reactions through CA C H T U N G T R E N N U N G (sp 3 ) À N bond cleavage, [3,12] we envisioned that the NH 2 group in primary allylic amines would be activated dramatically by hypophosphorous acid or H-phosphinic acids to facilitate allylic CÀN bond cleavage with palladium(0), and that the resulting p-allylpalladium and phosphinate species would form C À P bonds to give allylic-(H)-phosphinic acids (Scheme 1).…”

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Catalytic Allylation of Hypophosphorous Acid and H‐Phosphinic Acids with Primary Allylic Amines

Zhou

Chen

et al. 2014

Asian J Org Chem

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Primary allylic amines serve as suitable allylic electrophiles for the allylation reactions of hypophos-A C H T U N G T R E N N U N G phorous acid and H-phosphinic acids. In the presence of tris(dibenzylideneacetone)dipalladium(0) ([Pd 2 A C H T U N G T R E N N U N G (dba) 3 ], 0.1 mol %) and Xantphos (0.2 mol %), aqueous hypophosphorous acid was allylated by a-unbranched primary allylic amines in a highly regioselective fashion to give structurally diverse allylic H-phosphinic acids in good to excellent yields with exclusive E selectivity. Moreover, increasing the catalyst loading to 1 mol % and adding aqueous phosphoric acid (1.2 equiv.) permitted the allylation of H-phosphinic acids with a-unbranched primary allylic amines to proceed to give disubstituted phosphinic acids in good to excellent yields.Allylic halides and alcohol derivatives frequently serve as electrophilic components in the Tsuji-Trost reaction, which is powerful for the synthesis of unsaturated compounds. [1] While allylic amines have rarely been used directly as allylic electrophiles because of the poor leaving ability of amino groups, [2] it would be rewarding to develop the Tsuji-Trost reaction with allylic amines to explore new reactivity and selectivity. It is noteworthy that, in general, the synthetic routes to allylic amines are not longer than those to allylic halides and alcohol derivatives. Allylic amines can be prepared by reduction of a,b-unsaturated amides or nitriles by reductive amination of a,b-unsaturated carbonyl compounds or by modification of allylamines through the Heck reaction.[3] Moreover, the basicity of allylic amines permits their purification in large quantities by simple extractive procedures instead of routine chromatography. Sporadic studies have shown that allylic amines, in most cases secondary and tertiary ones, can undergo the Tsuji-Trost reaction with a few types of carbon, [3b-d, 4] nitrogen, [5] and sulfur nucleophiles. [3a,e, 6, 7] To the best of our knowledge, there is no previous report on the Tsuji-Trost reaction of allylic amines with phosphorus nucleophiles. Herein, we report efficient allylation reactions of hypophosphorous acid and Hphosphinic acids with primary allylic amines, which are more atom-economic relative to those with commonly used allylic electrophiles because ammonia is the sole byproduct.The Tsuji-Trost reaction has been successfully extended to the allylation of a few phosphorus nucleophiles for the synthesis of allylic-(H)-phosphinic acids and their derivatives.[8] Montchamp and co-workers reported that hypophosphorous acid, hypophosphite salts, [9] and H-phosphinic acids [10] could undergo palladium-catalyzed allylation with allylic alcohols, esters, and carbonates.[11] When allylic alcohols were used as the allylic electrophiles, they underwent Fischer-like esterification prior to palladium-catalyzed C À O bond cleavage. Inspired by these reports, together with our interest in exploring new reactions through CA C H T U N G T R E N N U N G (sp 3 ) À N bond cleavage...

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Phosphorus‐Carbon Bond Formation: Palladium‐Catalyzed Cross‐Coupling of H‐Phosphinates and Other P(O)H‐Containing Compounds

Cited by 133 publications

References 136 publications

Manganese‐Mediated Intermolecular Arylation of H‐Phosphinates and Related Compounds

Manganese‐Mediated Intermolecular Arylation of H‐Phosphinates and Related Compounds

Phosphinate-containing heterocycles: A mini-review

Catalytic Allylation of Hypophosphorous Acid and H‐Phosphinic Acids with Primary Allylic Amines

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