A modular phosphate tether-mediated divergent strategy to complex polyols

• Paul R. Hanson,
• Susanthi Jayasinghe,
• Soma Maitra,
• Cornelius N. Ndi and
• Rambabu Chegondi

Beilstein J. Org. Chem. 2014, 10, 2332–2337, doi:10.3762/bjoc.10.242

• five polyol fragments. Each of the product polyols bears a central 1,3-anti-diol subunit with differential olefinic geometries at the periphery. Keywords: phosphate-tether; one-pot; sequential processes; organophosphorus; polyol; stereodivergent; Introduction 1,3-anti-Diol subunits are a central

Chiral phosphines in nucleophilic organocatalysis

• Yumei Xiao,
• Zhanhu Sun,
• Hongchao Guo and
• Ohyun Kwon

Beilstein J. Org. Chem. 2014, 10, 2089–2121, doi:10.3762/bjoc.10.218

• carbonates, Michael additions, γ-umpolung additions, and acylations of alcohols. Keywords: asymmetric catalysis; chiral phosphine; nucleophilic; organocatalysis; organophosphorus; synthesis; Introduction During the past two decades, tertiary phosphine catalysts have been applied extensively in a wide range

Organophosphorus chemistry

• Paul R. Hanson

Beilstein J. Org. Chem. 2014, 10, 2087–2088, doi:10.3762/bjoc.10.217

• Paul R. Hanson Department of Chemistry, University of Kansas, 1251 Wescoe Hall Drive, Lawrence, KS 66045-7582, USA 10.3762/bjoc.10.217 Keywords: organophosphorus; Organophosphorus compounds are ubiquitous in nature, and due to their innate chemical properties, serve a fundamental role in a

• heights. This Thematic Series highlights and details some of the novel methods that are advancing the field of organophosphorus chemistry. The Thematic Series covers topics that range from new synthetic methods and phosphorus-based ligands in asymmetric catalysis to bisphosphonates as promising enzyme

• phosphanylidenecarbenes and phosphoryl azides, and bisphosphonate ethers as promising inhibitors of geranylgeranyl diphosphate synthase (GGDPS). The articles and reviews capture the emerging potential of organophosphorus compounds and exciting opportunities in the field, and hopefully, will inspire and motivate

P(O)R₂-directed Pd-catalyzed C–H functionalization of biaryl derivatives to synthesize chiral phosphorous ligands

• Rong-Bin Hu,
• Hong-Li Wang,
• Hong-Yu Zhang,
• Heng Zhang,
• Yan-Na Ma and
• Shang-dong Yang

Beilstein J. Org. Chem. 2014, 10, 2071–2076, doi:10.3762/bjoc.10.215

• products are produced with good enantioselectivity. Keywords: chiral synthesis; Pd-catalysis; organophosphorus; phosphorus ligands; P(O)R2-directing; Introduction In the past decades, phosphorus ligands have been demonstrated to be efficient ligands in many metal-catalyzed organic reactions [1][2][3][4

Photorelease of phosphates: Mild methods for protecting phosphate derivatives

• Sanjeewa N. Senadheera,
• Abraham L. Yousef and
• Richard S. Givens

Beilstein J. Org. Chem. 2014, 10, 2038–2054, doi:10.3762/bjoc.10.212

• to completion. The 2,6-naphthyl ketone platform instead remains intact whereas the quinolin-5-yl ketone fragments to a much more complex, highly absorbing reaction mixture that competes for the incident light. Keywords: caged phosphates; hydroxynaphthylacetyl; organophosphorus; photo-Favorskii

Application of cyclic phosphonamide reagents in the total synthesis of natural products and biologically active molecules

• Thilo Focken and
• Stephen Hanessian

Beilstein J. Org. Chem. 2014, 10, 1848–1877, doi:10.3762/bjoc.10.195

• summarized, as well as an overview of the synthesis of the employed phosphonamide reagents. Keywords: conjugate addition; cyclopropanation; olefination; organophosphorus; phosphonamide; total synthesis; Introduction Chiral non-racemic and achiral cyclic phosphonamide reagents 1–7 (Figure 1) have been

Rational design of cyclopropane-based chiral PHOX ligands for intermolecular asymmetric Heck reaction

• Marina Rubina,
• William M. Sherrill,
• Alexey Yu. Barkov and
• Michael Rubin

Beilstein J. Org. Chem. 2014, 10, 1536–1548, doi:10.3762/bjoc.10.158

• the isomerization were identified. It was shown that the nature of this isomerization is different from that demonstrated previously using chiral diphosphine ligands. Keywords: asymmetric catalysis; chiral phosphine ligands; cyclopropane; Heck reaction; organophosphorus; transition metal catalysis

Rasta resin–triphenylphosphine oxides and their use as recyclable heterogeneous reagent precursors in halogenation reactions

• Xuanshu Xia and
• Patrick H. Toy

Beilstein J. Org. Chem. 2014, 10, 1397–1405, doi:10.3762/bjoc.10.143

• halogenated products in high yields after simple purification. The polymer-supported triphenylphosphine oxides formed as a byproduct during these reactions could be recovered and reused numerous times with no appreciable decrease in reactivity. Keywords: Appel reaction; halogenation; organophosphorus

Synthesis of chiral N-phosphoryl aziridines through enantioselective aziridination of alkenes with phosphoryl azide via Co(II)-based metalloradical catalysis

• Jingran Tao,
• Li-Mei Jin and
• X. Peter Zhang

Beilstein J. Org. Chem. 2014, 10, 1282–1289, doi:10.3762/bjoc.10.129

• ; cobalt complex; metalloradical catalysis; organophosphorus; phosphoryl azide; Introduction Aziridines, the smallest three-membered nitrogen-containing heterocycles, are highly valuable heterocyclic compounds that are widely used in organic synthesis and pharmaceuticals [1][2]. As a result, tremendous

Synthesis of 1-[bis(trifluoromethyl)phosphine]-1’-oxazolinylferrocene ligands and their application in regio- and enantioselective Pd-catalyzed allylic alkylation of monosubstituted allyl substrates

• Zeng-Wei Lai,
• Rong-Fei Yang,
• Ke-Yin Ye,
• Hongbin Sun and
• Shu-Li You

Beilstein J. Org. Chem. 2014, 10, 1261–1266, doi:10.3762/bjoc.10.126

• range of substrates. Keywords: allylic substitution; enantioselectivity; ferrocene; organophosphorus; palladium; regioselectivity; Introduction The palladium-catalyzed asymmetric allylic alkylation (AAA) reaction is now becoming an efficient method for the construction of carbon–carbon bonds [1][2][3

Atherton–Todd reaction: mechanism, scope and applications

• Stéphanie S. Le Corre,
• Mathieu Berchel,
• Hélène Couthon-Gourvès,
• Jean-Pierre Haelters and
• Paul-Alain Jaffrès

Beilstein J. Org. Chem. 2014, 10, 1166–1196, doi:10.3762/bjoc.10.117

• for biological applications. The selected examples to illustrate the applications of the Atherton–Todd reaction mainly cover the past 15 years. Keywords: amphiphiles; flame retardant; lipid conjugates; organophosphorus; phosphoramidate; phosphate; Review 1. Introduction The reaction of

• established. From a stereochemical point of view, these results can be summarized as shown in Scheme 7-v. Other recent studies have reported stereocontrolled AT reactions. Han et al. [33] described the preparation of optically active organophosphorus acid derivatives from menthyl-based H-phosphinates (or

Preparation of phosphines through C–P bond formation

• Iris Wauters,
• Wouter Debrouwer and
• Christian V. Stevens

Beilstein J. Org. Chem. 2014, 10, 1064–1096, doi:10.3762/bjoc.10.106

• ; enantioselectivity; hydrophosphination; organophosphorus chemistry; phosphines; phosphine-boranes; substitution reactions; trivalent phosphorus; Introduction Phosphines are an important class of organophosphorus compounds. They are often used as ligands in metal complex catalysis and they have become a popular

Theoretical studies on the intramolecular cyclization of 2,4,6-t-Bu₃C₆H₂P=C: and effects of conjugation between the P=C and aromatic moieties

• Masaaki Yoshifuji and
• Shigekazu Ito

Beilstein J. Org. Chem. 2014, 10, 1032–1036, doi:10.3762/bjoc.10.103

• : suggests remarkable conjugation effects between the nearly coplanar P=C skeleton and the aryl moiety. Keywords: 3,4-dihydro-1-phosphanaphthalene; intramolecular cyclization; organophosphorus; phosphanylidenecarbene; steric protection; theoretical calculation; Introduction Sterically demanding groups on

• number of unique organophosphorus compounds [5][6]. The phosphorus version of Fritsch–Buttenberg–Wiechell (FBW) reaction [7][8][9][10] of Mes*P=C(X)Li (X = halogen, Mes* = 2,4,6-t-Bu3C6H2) affording an air-stable phosphaalkyne Mes*C≡P is a typical example for understanding the chemistry of a

Allenylphosphine oxides as simple scaffolds for phosphinoylindoles and phosphinoylisocoumarins

• G. Gangadhararao,
• Ramesh Kotikalapudi,
• M. Nagarjuna Reddy and
• K. C. Kumara Swamy

Beilstein J. Org. Chem. 2014, 10, 996–1005, doi:10.3762/bjoc.10.99

• . Interestingly, in the presence of wet trifluoroacetic acid, in addition to phosphinoylisocoumarins, phosphorus-free isocoumarins were also obtained. Key products were characterized by single crystal X-ray crystallography. Keywords: allenes; indoles; isocoumarins; organophosphorus; phosphinoyl-heterocycles

Synthesis of fluorescent (benzyloxycarbonylamino)(aryl)methylphosphonates

• Michał Górny vel Górniak,
• Anna Czernicka,
• Piotr Młynarz,
• Waldemar Balcerzak and
• Paweł Kafarski

Beilstein J. Org. Chem. 2014, 10, 741–745, doi:10.3762/bjoc.10.68

• (benzyloxycarbonylamino)(aryl)methylphosphonic acids is described by means of the Oleksyszyn reaction. The library was enlarged by the application of a Suzuki–Miayra approach and by preparation of mixed esters. Keywords: aminophosphonates; Oleksyszyn reaction; organophosphorus; Z-aminophosphonate esters; Introduction

Phosphinate-containing heterocycles: A mini-review

• Olivier Berger and
• Jean-Luc Montchamp

Beilstein J. Org. Chem. 2014, 10, 732–740, doi:10.3762/bjoc.10.67

• rare. The growing availability of synthetic methods will undoubtedly change this situation in the near future. Keywords: amino acid; heterocyle; organophosphorus; phosphinic; phosphorus; Introduction The preparation of P-heterocycles has been the subject of many studies over the years, and the field

• organophosphorus compounds: the phosphinates R1R2P(O)(OR) [9]. Because the phosphinic acid moiety P(O)OH can mimic carboxylic acids, its incorporation into heterocycles may offer new opportunities for the discovery of biologically active analogs. However, little or no biological data is available at this time

Cyclic phosphonium ionic liquids

• Sharon I. Lall-Ramnarine,
• Joshua A. Mukhlall,
• James F. Wishart,
• Robert R. Engel,
• Alicia R. Romeo,
• Masao Gohdo,
• Sharon Ramati,
• Marc Berman and
• Sophia N. Suarez

Beilstein J. Org. Chem. 2014, 10, 271–275, doi:10.3762/bjoc.10.22

• less conductive and have slightly smaller self-diffusion coefficients than their cyclic ammonium congeners. Keywords: cyclic phosphonium; ionic liquid; organophosphorus; phosphinanium; phospholanium; phosphonium; Introduction The most widely investigated and commercially available ionic liquids (ILs

Homolytic substitution at phosphorus for C–P bond formation in organic synthesis

• Hideki Yorimitsu

Beilstein J. Org. Chem. 2013, 9, 1269–1277, doi:10.3762/bjoc.9.143

• Hideki Yorimitsu Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan ACT-C, Japan Science and Technology Agency, Sakyo-ku, Kyoto 606-8502, Japan 10.3762/bjoc.9.143 Abstract Organophosphorus compounds are important in organic chemistry. This

• review article covers emerging, powerful synthetic approaches to organophosphorus compounds by homolytic substitution at phosphorus with a carbon-centered radical. Phosphination reagents include diphosphines, chalcogenophosphines and stannylphosphines, which bear a weak P–heteroatom bond for homolysis

• . This article deals with two transformations, radical phosphination by addition across unsaturated C–C bonds and substitution of organic halides. Keywords: addition; free radical; homolysis; phosphine; radical; substitution; Introduction Organophosphorus compounds constitute an important class of

Asymmetric Diels–Alder reaction with >C=P– functionality of the 2-phosphaindolizine-η¹-P-aluminium(O-menthoxy) dichloride complex: experimental and theoretical results

• Rajendra K. Jangid,
• Nidhi Sogani,
• Neelima Gupta,
• Raj K. Bansal,
• Moritz von Hopffgarten and
• Gernot Frenking

Beilstein J. Org. Chem. 2013, 9, 392–400, doi:10.3762/bjoc.9.40

• phosphinine [15]. We recently compiled a review on the DA reactions involving the >C=P– functionality of various organophosphorus compounds wherein all these aspects have been discussed [16]. During the past few years, we have investigated the DA reaction with the >C=P– functionality of 1,3-azaphospholes

Inclusion of the insecticide fenitrothion in dimethylated-β-cyclodextrin: unusual guest disorder in the solid state and efficient retardation of the hydrolysis rate of the complexed guest in alkaline solution

• Dyanne L. Cruickshank,
• Natalia M. Rougier,
• Raquel V. Vico,
• Susan A. Bourne,
• Elba I. Buján,
• Mino R. Caira and
• Rita H. de Rossi

Beilstein J. Org. Chem. 2013, 9, 106–117, doi:10.3762/bjoc.9.14

• Orgánica, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Ciudad Universitaria, X5000HUA, Córdoba, Argentina 10.3762/bjoc.9.14 Abstract An anhydrous 1:1 crystalline inclusion complex between the organophosphorus insecticide fenitrothion [O,O-dimethyl O-(3-methyl-4-nitrophenyl

• pesticide against undesired degradation reactions. Fenitrothion [O,O-dimethyl O-(3-methyl-4-nitrophenyl)phosphorothioate] (1, Figure 1) is an organophosphorus insecticide and acaricide [3]. It is effective against a wide range of pests that damage forests and various crops and it can also be used in the

• ]. In our recent reports on the interaction between CDs and the organophosphorus insecticide 1 we gave an account of the X-ray crystal structures and thermal decomposition profiles of two solid inclusion complexes between permethylated α- and β-cyclodextrins, hexakis(2,3,6-tri-O-methyl)-α-CD (TRIMEA

Valence isomerization of cyclohepta-1,3,5-triene and its heteroelement analogues

• Helen Jansen,
• J. Chris Slootweg and
• Koop Lammertsma

Beilstein J. Org. Chem. 2011, 7, 1713–1721, doi:10.3762/bjoc.7.201

• +G(d,p) level [7]. Also for the phosphepine system [108], benzannulation leads to interesting targets. Namely, the thermal lability of the transition-metal-complexed 3H-benzophosphepine 33 was explored by Lammertsma et al. for the synthesis of a variety of organophosphorus compounds by means of [1

Aromatic and heterocyclic perfluoroalkyl sulfides. Methods of preparation

• Vladimir N. Boiko

Beilstein J. Org. Chem. 2010, 6, 880–921, doi:10.3762/bjoc.6.88

• have appeared which make use of novel intermediates. Thus, single-electron oxidation or reduction enables the generation of perfluoroalkyl radicals. Two-electron reduction of perfluoroalkyl iodides generates perfluoroalkyl carbanions, which may be stabilized by organophosphorus and organosilicon

Chiral trimethylsilylated C₂-symmetrical diamines as phosphorous derivatizing agents for the determination of the enantiomeric excess of chiral alcohols by ¹H NMR

• Anne-Sophie Chauvin and
• Alexandre Alexakis

Beilstein J. Org. Chem. 2006, 2, No. 6, doi:10.1186/1860-5397-2-6

• Anne-Sophie Chauvin Alexandre Alexakis École Polytechnique Fédérale de Lausanne, LCSL, BCH 1405, CH-1015 Lausanne, Switzerland Department of Organic Chemistry, University of Geneva, 30, quai Ernest Ansermet, CH-1211 Geneva 4, Switzerland 10.1186/1860-5397-2-6 Abstract The use of organophosphorus

Synthesis of phosphorothioates using thiophosphate salts

• Babak Kaboudin and
• Fatemeh Farjadian

Beilstein J. Org. Chem. 2006, 2, No. 4, doi:10.1186/1860-5397-2-4

• alumina under solvent-free conditions using microwave irradiation. Introduction Organophosphorus compounds have found a wide range of application in the areas of industrial, agricultural, and medicinal chemistry owing to their biological and physical properties as well as their utility as synthetic

• the utility of surface-mediated reactions for the synthesis of organophosphorus compounds, [37][38][39][40][41][42][43][44][45][46][47][48] we report a new method for the preparation of phosphorothioates by reaction of diethyl phosphite with alkyl halides in the presence of a mixture of ammonium

• group (hard electrophilic center) gives the O-acylation product. As a part of our efforts to explore the utility of surface-mediated reactions for the synthesis of organophosphorus compounds, [16][17][18] herein we report a new method for the preparation of phosphorothioates by reaction of diethyl