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. 2024 May 12;26(29):6071–6075. doi: 10.1021/acs.orglett.4c01190

Bis(bicyclo[1.1.1]pentyl)chlorophosphine as a Precursor for the Preparation of Bis(bicyclo[1.1.1]pentyl)phosphines

Griffin L Perry 1, Nathan D Schley 1,*
PMCID: PMC11287751  PMID: 38735051

Abstract

graphic file with name ol4c01190_0003.jpg

Dialkylchlorophosphines are among the most versatile building blocks for tertiary phosphine ligands, but their synthesis relies on the nucleophilic substitution of PCl3, leaving substituents that require P–H precursors largely inaccessible. The primary phosphine reagent iPr2NPH2·BH3 can serve as a doubly protected PH2Cl proxy, enabling the synthesis of bis(bicyclo[1.1.1]pentyl)chlorophosphine (Bcp2PCl) for the first time. Bcp2PCl serves as a general reagent for the preparation of a family of bis(bicyclo[1.1.1]pentyl) alkyl- and arylphosphines, including new members of privileged phosphine ligand scaffolds.

Introduction. Organophosphines are among the most commonly employed ligands in organometallic chemistry, contributing to the efficacy of nearly every major class of transformations performed with homogeneous catalysis. For many transformations, so-called “privileged” ligand classes have emerged that tend to confer either exceptional catalyst performance or unusual substrate generality.1 Since minor modifications to a ligand’s structure can dramatically impact reactivity in ways that are difficult to predict,2 the availability of privileged ligand classes for a transformation can be viewed as necessary to the wide adoption of that transformation by the synthetic chemistry community. Most privileged phosphine ligands follow the general form R2PR′ with R being a common substituent (e.g., iPr, Ph, tBu, Cy) and R′ being the distinguishing fragment. Dialkylbiarylphosphines developed by Buchwald are a canonical example, as modification of the ligand’s biaryl or dialkyl substituents has led to highly effective catalysts, often optimized for a particular substrate class.1b Many privileged diphosphines follow a similar formula including ferrocenyl diphosphines3 (e.g., dppf, MandyPhos,4 and Josiphos5 ligands), binap,6 spirobiindane,7 and SEGPHOS8 derivatives. In nearly all cases, the final phosphine is synthesized by nucleophilic addition to an electrophilic dialkylchlorophosphine derivative. Thus, much of the expansive literature on dialkylphosphines depends on the availability of suitable dialkylchlorophosphine building blocks for the continued development of new and effective catalytic systems.

In a recent report we described the synthesis and applications of tris(bicyclo[1.1.1]pentyl)phosphine (PBcp3) in palladium-catalyzed sp3-electrophile cross-coupling reactions.2c The bicyclo[1.1.1]pentyl group was first introduced in organophosphorus chemistry with Wiberg’s synthesis of Ph2P(Bcp) in 19909 but has remained largely unexplored as a substituent in phosphine ligands for transition metal complexes. The lack of a direct route to bicyclo[1.1.1]pentyllithium or Grignard reagents leaves radical addition of P–H bonds across the reactive C–C bond of [1.1.1]propellane as the most suitable route for bicyclo[1.1.1]pentyl phosphine synthesis.2c,9,10 Indeed, our synthesis of PBcp3 relied on the radical alkylation of PH3. Adapting this route to an expansive collection of bis(bicyclo[1.1.1]pentyl) derivatives of privileged phosphine scaffolds would require the synthesis of the corresponding primary phosphine in each case. Very few primary phosphines are commercially available owing to their stench and extreme oxygen sensitivity.8 Still, our observation that bicyclo[1.1.1]pentyl substituents impart desirable properties of stability, crystallinity, compact steric profile, and electron donor power to the resulting ligand2c have encouraged a search for an alternative, convergent strategy.

Results and Discussion.

Since the majority of organophosphine synthetic routes to privileged phosphines rely on the availability of dialkylchlorophosphines, we aimed to develop a synthetic route to chlorobis(bicyclo[1.1.1]pentyl)phosphine (Bcp2PCl). As radical addition of a P–H bond to [1.1.1]propellane currently represents the most direct means of introducing the bicyclo[1.1.1]pentyl moiety, we canvassed the literature for suitable phosphorus starting materials. Phosphinous chloride (PH2Cl) has no appreciable lifetime in the condensed phase,11 likely stemming from the incompatibility of chlorophosphines with primary or secondary phosphine P–H bonds. For instance, PPh2Cl reacts with PPh2H to give tetraphenyldiphosphine12 and treatment of PH3 with dilute chlorine gives P2H4.13 At the same time, there are very few protected primary phosphorus(III) derivatives available with the exception of Me3SiPH2, whose synthesis begins at PH3 via the corresponding phosphide.14 PH3’s toxicity and flammability are manageable, especially on small scales,2c,15 but we posited that its use here would limit the number of researchers willing to explore bis(bicyclo[1.1.1]pentyl)phosphine derivatives and so have endeavored to find an alternate strategy.

Recently, Slootweg and co-workers described the synthesis of a series of primary amidophosphine boranes (RPH2·BH3) via reduction of the corresponding amidodichlorophosphine with lithium borohydride.16 By this method, they were able to prepare iPr2NPH2·BH3, which we posited could serve as a rare example of a stable PH2Cl synthon. To our delight, iPr2NPH2·BH3 undergoes UV-promoted alkylation by [1.1.1]propellane to give the (diisopropylamido)bis(bicyclo[1.1.1]pentyl)phosphine borane (Bcp2PNiPr2·BH3) (1) as a stable, colorless solid (Figure 1, A).

Figure 1.

Figure 1

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A) Synthesis of Bcp2PCl (2) from Slootweg’s iPr2NPH2·BH3. B–E) Applications of 2 in the synthesis of tertiary phosphines. F) Reduction of 2 to the diphosphine. Right: ORTEPs of 3·BH3, 4, 5, 6, and 7 are shown at 50% probability.

Bcp2PNiPr2·BH3 can be converted into the desired chlorophosphine through a two-step sequence. Borane deprotection with diethylamine gives the putative amidodialkylphosphine Bcp2PNiPr2, which can be chlorinated directly without isolation using ethereal HCl (Figure 1, A).17 The chlorophosphine Bcp2PCl (2) is conveniently purified by Kugelrohr distillation to give the product as a colorless oil. Thus, Bcp2PCl is accessible in four steps from commercially available compound iPrN2PCl or five steps from PCl3. This route avoids the need for PH3 and validates Slootweg’s amidophosphine borane iPr2NPH2·BH3 as a convenient PH2Cl synthon.

With a suitable and scalable route to Bcp2PCl in hand, we set about exploring its versatility as a building block for the synthesis of an array of organophosphorus compounds. Treatment of Bcp2PCl with MeMgBr gives the tertiary phosphine Bcp2PMe (3) as a colorless oil (Figure 1, part B). This straightforward procedure exemplifies the necessity of our having developed a route to Bcp2PCl, since synthesis of Bcp2PMe would have otherwise required radical alkylation of MePH2 with propellane. MePH2 is a pyrophoric gas and its protected analogue MePH2·BH3 is a volatile liquid.18 Bcp2PMe can be conveniently converted to a crystalline solid by protection as the BH3 adduct. Secondary alkyl Grignards are also compatible reagents, as in the reaction of cyclobutyl magnesium bromide with Bcp2PCl to give cyclobutyl bis(bicyclo[1.1.1]pentyl)phosphine (Bcp2PCyb, 4) as a colorless solid (Figure 1, C). Related trialkylphosphines can be highly effective ligands for enabling difficult oxidative addition reactions at Pd.2b,2c The Bcp group has in common with tBu rigorous 3-fold symmetry and a lack of conformational flexibility that few other substituents possess. Computational predictions19 of steric and electronic Tolman parameters20 place Bcp2PCyb (4) (163.2°, 2058.6 cm–1) as similar in size and donor power to PiPr3 (160.0°, 2059.2 cm–1). Bcp2PMe (3) (158.2°, 2061.3 cm–1) is smaller and slightly less donating than the related phosphine tBu2PMe (164.2°, 2059),21 being closer to PEt3 (132.0°, 2061.7 cm–1) in donor power.2c,20

Bis(bicyclo[1.1.1]pentyl) arylphosphines are also accessible from Bcp2PCl. Lithiation of o-(2,4,6-triisopropylphenyl)phenyl iodide followed by treatment with Bcp2PCl gives 5, the bis(bicyclo[1.1.1]pentyl) analogue of XPhos (Figure 1, D).22 Related dialkylbiarylphosphine ligands have been effectively utilized in a variety of cross-couplings and aminations.1b Bcp2PCl can also be used in the preparation of bidentate bis(bicyclo[1.1.1]pentyl) derivatives. For example, treatment of Li2Fc·TMEDA with Bcp2PCl provides 6, the bicyclopentyl analogue of dppf, (Bcp2P)2Fc (Figure 1, E). Dppf variants are commonly applied in Ni- and Pd-catalyzed transformations and are generally considered a privileged ligand class.1c,23 The properties of (Bcp2P)2Fc are being explored in ongoing efforts.

Bcp2PCl also has potential applications beyond tertiary phosphine synthesis. Treatment with magnesium turnings12d gives the diphosphine Bcp4P2 (7) as the exclusive product without evidence for reductive C–C or C–P bond scission of the strained carbocyclic skeleton (Figure 1, F). Analogous diphosphines are useful reagents in diphosphination reactions.12c,24

Bcp2PCl also undergoes reduction with LiBH4 to give the corresponding borane-protected secondary phosphine Bcp2PH·BH3 (8) (Figure 2). In our previous report2c we showed that alkylation of PH3 with [1.1.1]propellane proceeds to PBcp3 even in the presence of excess PH3; therefore, reduction of Bcp2PCl provides the only current means to access this protected secondary phosphine. Secondary phosphines are more air-sensitive than their corresponding chlorophosphines and have a disagreeable odor, but these downsides are tempered by protection of the borane adduct. We have successfully employed Bcp2PH·BH3 in the preparation of the so-called PCP pincer ligand Bcp4PCP (9). Under phase-transfer conditions25 Bcp2PH·BH3 serves as a nucleophilic phosphine reagent, which gives Bcp4PCP after deprotection. This procedure gave the highest yields of several we explored (Figure 2).

Figure 2.

Figure 2

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Synthesis and an application of the protected 2° phosphine Bcp2PH·BH3 (8), (top). ORTEPs of 8 (bottom left) and 9·2BH3 (bottom right) are shown at 50% probability.

Conclusions.

Slootweg’s phosphine reagent iPr2NPH2·BH3 serves as a doubly protected proxy for phosphinous chloride (PH2Cl), a species that is inaccessible in the condensed phase. Radical addition of [1.1.1]propellane followed by halogenation gives bis(bicyclo[1.1.1]pentyl)chlorophosphine. This precursor is easily prepared on gram scales and provides straightforward access to a host of bis(bicyclo[1.1.1]pentyl) alkyl- and arylphosphines, including members of privileged phosphine ligand scaffolds. We expect that this route will improve the availability of Bcp phosphine derivatives in catalytic studies and will provide a route to other chlorophosphines that would benefit from a PH2Cl synthon, for instance, those derived of olefin hydrophosphination.26 Our ongoing work aims to more broadly explore the applications of bis(bicyclo[1.1.1]pentyl)phosphine ligands in catalysis.

Acknowledgments

Funding from Vanderbilt University is gratefully acknowledged. This material is based upon work supported by the National Science Foundation under grant no. CHE-1847813.

Data Availability Statement

The data underlying this study are available in the published article and its Supporting Information.

Supporting Information Available

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.orglett.4c01190.

  • Experimental procedures, summaries of computational and experimental results, compound characterization data, NMR and IR spectra, and X-ray crystallographic data (PDF)

  • Atomic coordinates (XYZ)

The authors declare no competing financial interest.

Supplementary Material

ol4c01190_si_001.pdf (1.9MB, pdf)
ol4c01190_si_002.xyz (7.7KB, xyz)

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Associated Data

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Supplementary Materials

ol4c01190_si_001.pdf (1.9MB, pdf)
ol4c01190_si_002.xyz (7.7KB, xyz)

Data Availability Statement

The data underlying this study are available in the published article and its Supporting Information.

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