Functionalization of P4 through Direct P-C Bond Formation

doi:10.1002/chem.201702067

Review

. 2017 Sep 4;23(49):11738-11746.

doi: 10.1002/chem.201702067. Epub 2017 Jul 27.

Functionalization of P₄ through Direct P-C Bond Formation

Jaap E Borger¹, Andreas W Ehlers^{1

2

3}, J Chris Slootweg^{1

3}, Koop Lammertsma^{1

2}

Affiliations

¹ Department of Chemistry and Pharmaceutical Sciences, Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV, Amsterdam, the Netherlands.
² Department of Chemistry, University of Johannesburg, Auckland Park, Johannesburg, 2006, South Africa.
³ Current address: Van "t Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH, Amsterdam, the Netherlands.

PMID: 28497639
PMCID: PMC5655700
DOI: 10.1002/chem.201702067

Review

Functionalization of P₄ through Direct P-C Bond Formation

Jaap E Borger et al. Chemistry. 2017.

. 2017 Sep 4;23(49):11738-11746.

doi: 10.1002/chem.201702067. Epub 2017 Jul 27.

Authors

Jaap E Borger¹, Andreas W Ehlers^{1

2

3}, J Chris Slootweg^{1

3}, Koop Lammertsma^{1

2}

Affiliations

¹ Department of Chemistry and Pharmaceutical Sciences, Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV, Amsterdam, the Netherlands.
² Department of Chemistry, University of Johannesburg, Auckland Park, Johannesburg, 2006, South Africa.
³ Current address: Van "t Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH, Amsterdam, the Netherlands.

PMID: 28497639
PMCID: PMC5655700
DOI: 10.1002/chem.201702067

Abstract

Research on chlorine-free conversions of P₄ into organophosphorus compounds (OPCs) has a long track record, but methods that allow desirable, direct P-C bond formations have only recently emerged. These include the use of metal organyls, carbenes, carboradicals, and photochemical approaches. The versatile product scope enables the preparation of both industrially relevant organophosphorus compounds, as well as a broad range of intriguing new compound classes. Herein we provide a concise overview of recent breakthroughs and outline the acquired fundamental insights to aid future developments.

Keywords: main group chemistry; nucleophilic addition; organophosphorus compounds; phosphorus; phosphorus anions.

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Figures

**Figure 1**
Preparation of organophosphorus compounds (OPCs) from P₄.

**Scheme 1**
Reactions of P₄ with organoalkali reagents. Mes*=2,4,6‐tBu₃C₆H₂, R¹=Bu, R²=Et or Pr, X=Br or Cl.

**Scheme 2**
Synthesis of LA‐stabilized [RP₄]⁻ butterfly anions and subsequent substitution and transfer reactions. Mes*=2,4,6‐ tBu₃C₆H₂, Dmp=2,6‐dimesitylphenyl.

**Scheme 3**
Selective [3+1]‐fragmentation reactions of LA‐stabilized RP₄ ⁻ butterfly **4 c**. Mes*=2,4,6‐tBu₃C₆H₂, IDipp=1,3‐bis(2,6‐diisopropylphenyl)‐imidazol‐2‐ylidene, CHD=cyclohexadiene.

**Scheme 4**
Functionalization of P₄ in the coordinated sphere of a coinage metal cation. Dipp=2,6‐diisopropylphenyl, Dmp=2,6‐dimesitylphenyl, pftb=perfluoro‐*tert*‐butoxy.

**Scheme 5**
Functionalization of P₄ by an n‐butylmagnesium complex. Dipp=2,6‐diisopropylphenyl.

**Scheme 6**
Functionalization of P₄ using solvent‐free mesityllithium.

**Scheme 7**
Direct preparation of phospholyl lithium derivatives from P₄.

**Scheme 8**
Functionalization of P₄ using p‐block organometallic compounds. Ar^Dipp2=2,6‐(2,6‐iPr₂C₆H₃)₂C₆H₃.

**Scheme 9**
Metal‐mediated direct P−C bond formation using (triphos)rhodium alkyl and aryl ethene complexes. Triphos=1,1,1‐tris(diphenylphosphanylmethyl)ethane, Tf=SO₃CF₃.

**Scheme 10**
Niobium‐mediated P−C bond formation. Ar=3,5‐Me₂C₆H₃, ²Ad=2‐adamantylidene.

**Scheme 11**
Reactivity of P₄ with CAACs. Dipp=2,6‐diisopropylphenyl.

**Scheme 12**
Reactivity of P₄ with various carbenes. Dipp=2,6‐diisopropylphenyl.

**Scheme 13**
Top: reactivity of P₄ with NHCs. Bottom: DFT computed mechanism for the formation of 36. NHC=1,3‐bis(2,6‐diisopropylphenyl)‐imidazolin‐2‐ylidene, Dipp=2,6‐diisopropylphenyl.

**Scheme 14**
Reactivity of P₄ with electrophilic NHCs.

**Scheme 15**
Three‐component reaction of P₄ with imidazolium salts and KOtBu. Dipp=2,6‐diisopropylphenyl.

**Scheme 16**
Functionalization of P₄ using a carbene–borane Lewis pair.

**Scheme 17**
Preparation of phosphonic acids from P₄ using Barton esters.

**Scheme 18**
Radical synthesis of tertiary‐ and cyclopolyphosphanes from P₄. Dmp=2,6‐dimesitylphenyl, Ar=3,5‐Me₂C₆H₃.

**Scheme 19**
Metal‐mediated radical synthesis of organyl‐substituted P₄ butterflies.

**Scheme 20**
Transfer of photochemically generated P₂ to1,3‐dienes.

**Scheme 21**
Reaction of P₄ with (trimethylsilyl)diazomethanide.

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References

1. Corbridge D. E. C., Phosphorus 2000, Elsevier, Amsterdam, 2000.
1. Hydrolysis of P4 with NaOH leads to NaH2PO2 and PH3, both of which can also be used to produce phosphorus compounds.
1. For reviews on the activation of P4 by main group compounds, see:
1. Scheer M., Balázs G., Seitz A., Chem. Rev. 2010, 110, 4236–4256; - PubMed
1. Giffin N. A., Masuda J. D., Coord. Chem. Rev. 2011, 255, 1342–1359.

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[1] Corbridge D. E. C., Phosphorus 2000, Elsevier, Amsterdam, 2000.

[2] Corbridge D. E. C., Phosphorus 2000, Elsevier, Amsterdam, 2000.

[3] Hydrolysis of P4 with NaOH leads to NaH2PO2 and PH3, both of which can also be used to produce phosphorus compounds.

[4] Hydrolysis of P4 with NaOH leads to NaH2PO2 and PH3, both of which can also be used to produce phosphorus compounds.

[5] For reviews on the activation of P4 by main group compounds, see:

[6] For reviews on the activation of P4 by main group compounds, see:

[7] Scheer M., Balázs G., Seitz A., Chem. Rev. 2010, 110, 4236–4256; - PubMed

[8] Scheer M., Balázs G., Seitz A., Chem. Rev. 2010, 110, 4236–4256; - PubMed

[9] Giffin N. A., Masuda J. D., Coord. Chem. Rev. 2011, 255, 1342–1359.

[10] Giffin N. A., Masuda J. D., Coord. Chem. Rev. 2011, 255, 1342–1359.

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Functionalization of P₄ through Direct P-C Bond Formation

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Functionalization of P₄ through Direct P-C Bond Formation

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