Improving the accuracy of ³¹P NMR chemical shift calculations by use of scaling methods

• William H. Hersh and
• Tsz-Yeung Chan

Beilstein J. Org. Chem. 2023, 19, 36–56, doi:10.3762/bjoc.19.4

• reference. 2. Calculation of chemical shifts. A small number of trivalent phosphorus compounds spanning a roughly 460 ppm chemical shift range was chosen initially to examine basis set effects, namely, PH3, PMeH2, PMe2H, PMe3, PPh3, P(OMe)3, methoxyphospholane (i.e., MeOP(OCH2CH2O)), and PCl3, each of which

• second set of tetracoordinate phosphorus compounds was then added to the trivalent set for scaling (Figure 1). In contrast to common trivalent phosphorus compounds, the chemical shifts of typical tetracoordinate analogues do not span such a large range, nor have calculations been routinely reported. A

• training set compounds and the calculation methods used (Table S4 in Supporting Information File 1). This resulted in extraordinarily linear fits for the trivalent phosphorus compounds spanning the full chemical shift range, and a bit more scatter of the tetracoordinate compounds over their smaller range

Comparison of crystal structure and DFT calculations of triferrocenyl trithiophosphite’s conformance

• Ruslan P. Shekurov,
• Mikhail N. Khrizanforov,
• Ilya A. Bezkishko,
• Tatiana P. Gerasimova,
• Almaz A. Zagidullin,
• Daut R. Islamov and
• Vasili A. Miluykov

Beilstein J. Org. Chem. 2022, 18, 1499–1504, doi:10.3762/bjoc.18.157

• phosphines, a relatively small number of trivalent phosphorus derivatives has been used to construct multiferrocene compounds. The use of ferrocene derivatives containing a phosphorus–sulfur bond is a promising direction, since coordination with a metal atom can occur both at the phosphorus and sulfur atoms

Highly regio- and stereoselective phosphinylphosphination of terminal alkynes with tetraphenyldiphosphine monoxide under radical conditions

• Dat Phuc Tran,
• Yuki Sato,
• Yuki Yamamoto,
• Shin-ichi Kawaguchi,
• Shintaro Kodama,
• Akihiro Nomoto and
• Akiya Ogawa

Beilstein J. Org. Chem. 2021, 17, 866–872, doi:10.3762/bjoc.17.72

• Innovation, Faculty of Agriculture, Saga University, 152-1 Shonan-cho, Karatsu, Saga 847-0021, Japan 10.3762/bjoc.17.72 Abstract The homolytic cleavage of the PV(O)–PIII bond in tetraphenyldiphosphine monoxide simultaneously provides both pentavalent and trivalent phosphorus-centered radicals with different

• reactivity of the P–P bond, therefore, when the combination of pentavalent phosphorus and trivalent phosphorus was examined, it was found that the desired radical addition of Ph2P(X)PPh2 (X = O, S) to alkenes successfully occurred [42][43] (Scheme 1c and 1d). However, in the case of Ph2P(O)PPh2, its

• . Noteworthy is that the capture of carbon radicals occurred only at the trivalent phosphorus site of Ph2P(O)PPh2. Therefore, the initiation step might also proceed via the attack of the carbon radical generated from V-40 at the trivalent phosphorus site to form Ph2P(O)• selectively. With this information in

Synthesis, structural characterization, and optical properties of benzo[f]naphtho[2,3-b]phosphoindoles

• Mio Matsumura,
• Takahiro Teramoto,
• Masato Kawakubo,
• Masatoshi Kawahata,
• Yuki Murata,
• Kentaro Yamaguchi,
• Masanobu Uchiyama and
• Shuji Yasuike

Beilstein J. Org. Chem. 2021, 17, 671–677, doi:10.3762/bjoc.17.56

• property; phosphorus; Introduction Phosphole-based heteroacenes are attracting increasing interest in various fields, such as organic synthesis, structural chemistry, and materials science [1][2][3][4]. The phosphorus atom of trivalent phosphorus compounds has a high chemical reactivity. Therefore, this

Synthesis and photophysical properties of novel benzophospholo[3,2-b]indole derivatives

• Mio Matsumura,
• Mizuki Yamada,
• Atsuya Muranaka,
• Misae Kanai,
• Naoki Kakusawa,
• Daisuke Hashizume,
• Masanobu Uchiyama and
• Shuji Yasuike

Beilstein J. Org. Chem. 2017, 13, 2304–2309, doi:10.3762/bjoc.13.226

• -effect transistors (OFETs) and luminescent materials [1][2][3][4][5][6][7][8][9]. The phosphorous atom of trivalent phosphorus compounds has a high chemical reactivity. Therefore, several reactions on the phosphorus atom such as oxidation, alkylation, and coordination to a Lewis acid can produce the

• may be associated with the low fluorescence quantum yields. Conclusion A series of novel indole-fused phospholes were synthesized by simple chemical modifications at the trivalent phosphorus center. These organophosphorus compounds generated a whole series of derivatives from only one precursor. The X

Nucleic acids through condensation of nucleosides and phosphorous acid in the presence of sulfur

• Tuomas Lönnberg

Beilstein J. Org. Chem. 2016, 12, 670–673, doi:10.3762/bjoc.12.67

• nucleic acid polymerizations described so far have utilized activated starting materials, such as cyclic phosphates [1][2] or phosphoroimidazolides [3][4]. The trivalent phosphorus atom of phosphorous acid is much more susceptible to a nucleophilic attack than the pentavalent phosphorus atom of phosphoric

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

• system of P(O)R2-directed Pd-catalyzed C–H activation. These compounds could be transformed to trivalent phosphorus compounds by silane to obtain the corresponding phosphorous ligands. Conclusion In summary, a series of substrates with axially chiral biaryl compounds containing a P(O)Ar2 directing group

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

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

• titanium complex (Scheme 23) [49]. This represents a unique direct method for preparing triorganophosphine without recourse to any trivalent phosphorus sources such as PCl3. Conclusion Introduction of a phosphorus atom by a radical process has offered an intriguing tool for the synthesis of

Methylidynetrisphosphonates: Promising C₁ building block for the design of phosphate mimetics

• Vadim D. Romanenko and
• Valery P. Kukhar

Beilstein J. Org. Chem. 2013, 9, 991–1001, doi:10.3762/bjoc.9.114

• prepared in good yield by the Arbuzov reaction of trimethylsilyl esters of trivalent phosphorus acids with the easily accessible 2,6-di-tert-butyl-4-(dichloromethyl)phenol. In the next step, the bisphosphonate 16 was oxidized with K3Fe(CN)6 into quinone methide 17 in 91% yield. Further addition of diethyl