Hypervalent Iodine-Based Activation of Triphenylphosphine for the Functionalization of Alcohols

Jasmin Eljo; Myriam S. Carle; Graham K. Murphy

doi:10.1055/s-0036-1589069

Synlett, Inhaltsverzeichnis

Synlett 2017; 28(20): 2871-2875
DOI: 10.1055/s-0036-1589069

letter

Hypervalent Iodine-Based Activation of Triphenylphosphine for the Functionalization of Alcohols

Jasmin Eljo

Department of Chemistry, University of Waterloo, 200 University Ave W., Waterloo, ON, N2L3G1, Canada graham.murphy@uwaterloo.ca

,

Myriam S. Carle

Department of Chemistry, University of Waterloo, 200 University Ave W., Waterloo, ON, N2L3G1, Canada graham.murphy@uwaterloo.ca

,

Graham K. Murphy *

Department of Chemistry, University of Waterloo, 200 University Ave W., Waterloo, ON, N2L3G1, Canada graham.murphy@uwaterloo.ca

› Institutsangaben

Abstract

Alle Artikel dieser Rubrik

Dedicated to Professor Victor Snieckus on the occasion of his 80^th birthday

Abstract

The use of hypervalent iodine reagents as a general tool for the activation of PPh₃ and its application to the functionalization of alcohols is reported. Combination of PPh₃ with PhICl₂ or TolIF₂ gives dihalophosphoranes that are characterized by ³¹P NMR, however, with PhIOAc₂, PhI(OTFA)₂, or the cyclic chloro(benzoyloxy)iodane, no phosphoranes were observed. Reaction of these iodanes with PPh₃ in the presence of primary, secondary, or tertiary alcohols results in either halogenation or acyl-transfer products in moderate to high yield.

Key words

Appel reaction - hypervalent iodine - halogenation - acylation - benzoylation

Volltext

Referenzen

References and Notes

1a Tian J. Gao WC. Zhou DM. Zhang C. Org. Lett. 2012; 14: 3020
1b Zhang C. Liu SS. Sun B. Tian J. Org. Lett. 2015; 17: 4106

2 Appel R. Angew. Chem., Int. Ed. Engl. 1975; 14: 801

3a Zhdankin VV. Stang PJ. Chem. Rev. 2002; 102: 2523
3b Wirth T. Hypervalent Iodine Chemistry: Modern Developments in Organic Synthesis. Springer; Berlin: 2003
3c Zhdankin VV. Stang PJ. Chem. Rev. 2008; 108: 5299
3d Yoshimura A. Zhdankin VV. Chem. Rev. 2016; 116: 3328
3e Zhdankin VV. Hypervalent Iodine Chemistry: Preparation Structure, and Synthetic Applications of Polyvalent Iodine Compounds. Wiley; Chichester: 2014

4a Tao J. Tran R. Murphy GK. J. Am. Chem. Soc. 2013; 135: 16312
4b Murphy GK. Abbas FZ. Poulton AV. Adv. Synth. Catal. 2014; 356: 2919
4c Coffey KE. Murphy GK. Synlett 2015; 26: 1003

5 Wright DW. Russell GA. Phenyliodine(III) Dichloride In e-EROS . Wiley; Hoboken, NJ: 2001

6a For syntheses of Ph₃PCl₂ with various reagents such as Cl₂, CCl₄, (COCl)₂, COCl₂, or C₂Cl₆, see: Michaelis A. Michaelis A. v. Soden H. Justus Liebigs Ann. Chem. 1885; 229: 295
6b Appel R. Angew. Chem., Int. Ed. Engl. 1975; 14: 801
6c Appel R. Geisler K. Scholer H. Chem. Ber. 1977; 110: 376

For NMR studies on the synthesis of 2 with C₂Cl₆, see:

6d Yin Q. Ye Y. Tang G. Zhao YF. Spectrochim. Acta, Part A 2006; 63: 192
6e Wiley GA. Stine WR. Tetrahedron Lett. 1967; 2321
6f Dillon KB. Lynch RJ. Reeve RN. Waddington TC. J. Chem. Soc. Dalton 1976; 1243
6g Appel R. Scholer H. Chem. Ber. 1977; 110: 2382

7a Kirk KL. Org. Process. Res. Dev. 2008; 12: 305
7b Bégué J.-P. Bonnet-Delpon D. Bioorganic and Medicinal Chemistry of Fluorine . John Wiley and Sons; Hoboken, NJ: 2008: 365
7c Ojima I. Fluorine in Medicinal Chemistry and Chemical Biology . Wiley-Blackwell; Chichester: 2009: 624

For syntheses of Ph₃PF₂ with various reagents such as XeF₂, SF₄, IF₅, DAST, COF₂, or HgF₂, see:

8a Kobayash Y. Akashi C. Chem. Pharm. Bull. 1968; 16: 1009
8b Frohn HJ. Maurer H. J. Fluorine Chem. 1986; 34: 73
8c Holmes RR. Chandrasekhar V. Day RO. Harland JJ. Payne JS. Holmes JM. Phosphorus Sulfur Relat. Elem. 1987; 30: 409
8d Gupta OD. Shreeve JM. J. Chem. Soc., Chem. Commun. 1984; 416
8e Doxsee KM. Hanawalt EM. Weakley TJ. R. Inorg. Chem. 1992; 31: 4420

9 Caputo CB. Winkelhaus D. Dobrovetsky R. Hounjet LJ. Stephan DW. Dalton Trans. 2015; 44: 12256
10 We believe its increased hydrolytic stability (relative Ph₃PCl₂) is due to the increased strength of P–F (490 kJ/mol) over P-Cl (326 kJ/mol) bonds.
11 Iranpoor N. Firouzabadi H. Davan EE. Tetrahedron Lett. 2013; 54: 1813
12 Gallos J. Varvoglis A. Chim. Chron., New Ser. 1987; 16: 87
13 Makowiec S. Rachon J. Heteroat. Chem. 2003; 14: 352
14 McNulty J. Capretta A. Laritchev V. Dyck J. Robertson AJ. Angew. Chem. Int. Ed. 2003; 42: 4051
15 Dormoy J.-R. Castro B. Triphenylphosphine Dichloride . In e-EROS . Wiley; Hoboken, NJ: 2001
16 Kobayashi Y. Akashi C. Chem. Pharm. Bull. 1968; 16: 1009

17a Mohandas TP. Mamman AS. Nair PM. Tetrahedron 1983; 39: 1187
17b Wicha J. Zarecki A. Kocór M. Tetrahedron Lett. 1973; 14: 3635

18 Taniguchi T. Hirose D. Ishibashi H. ACS Catal. 2011; 1: 1469
19 Carle MS. Shimokura GK. Murphy GK. Eur. J. Org. Chem. 2016; 3930
20 Reacting Ph₃PF₂ (4, 1.6 equiv) with 4-nitrophenethyl alcohol for 45 min at 160 °C using 10 mol% TiF₃ as an activating agent produced alkyl fluoride 5a in 66% yield.
21 The major competing reaction pathway in these experiments was alcohol dimerization, giving the ether. It is proposed that this arises from the alcohol outcompeting fluoride as the nucleophile. See ref. 16.
22 Zhang and co-workers reported phenethyl acetate to be the major byproduct of a reaction between 5, phenethyl alcohol, hexanoic acid, DMAP, and PPh₃. No indication of phenethyl trifluoroacetate was reported for the analogous reaction using iodane 7. See Table S1 in the supporting information of ref. 1a.
23 Only trace amounts of 15a or 15b were visible by ¹H NMR analysis of the crude reaction mixtures after 10 min. Prolonging the reaction times to 2–3 h did not significantly change the product ratios, suggesting that the reaction pathways are competing, as opposed to 14 reacting with the benzoate byproduct of the reaction to give 15. Concentrating the reaction mixtures before column chromatography appears to have increased the ratio of the benzoate products.
24 Zhdankin VV. Koposov AY. Litvinov DN. Ferguson MJ. McDonald R. Luu T. Tykwinski RR. J. Org. Chem. 2005; 70: 6484
25 Sample Experimental Procedure Into a conical flask was added the 4-phenyl-2-butanol (0.063 g, 0.42 mmol, 1 equiv) and CH₂Cl₂ (0.5 mL), and to this was added PPh₃ (1.1 equiv) and [bis(trifluoro-acetoxy)iodo]benzene (1.1 equiv). The reaction mixture was stirred at r.t. for 30 min, concentrated by rotary evaporation and subjected to column chromatography, where the stationary phase as acidified with 0.2% TFA in hexane. The crude reaction mixture was purified via column chromatography (10% EtOAc/hexane) to give 13c (0.066 g, 64% yield) as a colorless oil.¹⁹F NMR (282 MHz, CDCl₃): δ = –75.58. ¹H NMR (300 MHz, CDCl₃): δ = 7.34–7.16 (m, 5 H), 5.11 (m, 1 H), 2.74–2.60 (m, 2 H), 2.15–1.87 (m, 2 H), 1.39 (d, J = 6.3 Hz, 3 H);¹³C NMR (75 MHz, CDCl₃): δ = 157.1 (q, J = 41.5 Hz), 140.5, 128.6, 128.3, 126.3, 114.6 (q, J = 286.1 Hz), 75.8, 37.1, 31.4, 19.5.

Zusatzmaterial

Supporting Information