Addition Reactions of Tertiary Silylphosphanes with Acetylenic Ketones and Aldehydes

Martin  Reisser; Alexandra  Maier; Gerhard  Maas

doi:10.1055/s-2002-33533

LETTER

Addition Reactions of Tertiary Silylphosphanes with Acetylenic Ketones and Aldehydes

Martin Reisser, Alexandra Maier, Gerhard Maas*
Abteilung Organische Chemie I, Universität Ulm, Albert-Einstein-Allee 11, 89081 Ulm, Germany
Fax: +49(731)5022803; e-Mail: gerhard.maas@chemie.uni-ulm.de;

Abstract

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Abstract

(Trimethylsilyl)phosphanes Me₃Si-PR₂ (PR₂ = PPh₂, PEt₂, 1-phospholanyl) add smoothly across the C≡C bond of acetylenic ketones RCOC≡CPh to form (Z)-3-phosphanyl-2-(trimethylsilyl)prop-2-en-1-ones 3 (3,4-addition). Thermal isomerization of the latter yields the corresponding 3-(trimethylsilyl)oxy-allenylphosphane 6, formally the product of a 1,4-addition. Mainly 1,2-addition occurs with propiolic aldehydes leading to (1-[(trimethylsilyl)oxy]propargyl)phosphanes 4. Desilylation reactions of 3b yield either (3-oxopropyl)phosphanoxide 7 or (3-oxopropenyl)phosphanoxide 8.

Key words

organophosphorus(III) compounds - organosilicon compounds - nucleophilic addition at alkynones - enones - siloxy-allenes

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References

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<A NAME="RG16702ST-6C">6c</A> Fritz G. Poppenburg G. Rocholl MG. Naturwissenschaften 1962, 74: 255

1c Was obtained analogously form 1-phenyl- or 1H-phospholane.

(Z)-3-(Diphenylphosphanyl)-1,3-diphenyl-2-(trimethyl-silyl)prop-2-en-1-one(3a); general procedure: A solution of 1,3-diphenylprop-2-yn-1-one (2a, 3.1 g, 15.0 mmol) in THF (100 mL) was cooled at 0 °C and diphenyl(trimethyl-silyl)phosphane (1a, 3.87 g, 15.0 mmol) was added. The reaction mixture was kept with stirring at 0 °C for 2 h, then at 20 °C for 12 h. The solvent was evaporated at 15 mbar and the solid residue was recrystallized from CH₃CN to furnish 3a as colorless crystals (5.22 g, 75%), mp 127-128 °C. IR (KBr): 1663 s, 1243 s, 1233 s, 858 s, 842 s cm^-1. ¹H NMR (CDCl₃, 500.14 MHz): δ = 0.51 (d, ⁵ J _H,P = 1.2 Hz, 9 H, SiMe₃), 6.3-7.8 (20 H_Ph). MS (EI, 70 eV): m/z (%) = 466 (9), 465 (33), 464 (100) [all M⁺].
3b: From 1b and 2a; large pale-yellow crystals, 69% yield, mp 100 °C. IR (KBr): 1655 s, 1237 s, 844 s, 703 m cm^-1.
¹H NMR (CDCl₃, 500.14 MHz, 233 K): δ = 0.35 (d, ⁵ J _H,P = 1.6 Hz, 9 H, SiMe₃), 1.0-1.4 (m, 10 H_ethyl), 6.6-7.6 (10 H_Ph). ²⁹Si NMR (CDCl₃, 99.37 MHz): δ = -8.5 (d, ³ J _Si,P = 11.4 Hz). MS (EI, 70 eV): m/z (%) = 370 (5), 369 (10), 368 (39) [all M⁺], 279 (100). C₂₂H₂₉OSiP (368.53): calcd C 71.70, H 7.93; found C 71.38, H 8.12.
3c: From 1c and 2a; pale-yellow crystals, 69% yield, mp 99 °C. IR (KBr): 1667/1650 vs, 1230 vs, 1174 vs, 702 vs
cm^-1. ¹H NMR (CDCl₃, 500.14 MHz): δ = 0.35 (d, ⁵ J _H,P = 1.5 Hz, 9 H, SiMe₃), 1.08-1.25 (m, coalescing, 2 H), 1.35-1.45 (m, 2 H), 1.65-1.90 (m, 4 H), 6.7-7.7 (10 H_Ph). MS (EI, 70 eV): m/z (%) = 368 (2), 367 (7), 366 (25) [all M⁺], 279 (100). C₂₂H₂₇OPSi (366.51): calcd C 72.10, H 7.42; found C 71.80, H 7.55.
3d: From 1a and 2b; 70% yield, amorphous solid, mp 149 °C. IR (KBr): 1629 vs, 1413 s, 1261 s, 1246 s, 846 vs, 743 vs, 725 s, 702 vs cm^-1. ¹H NMR (CDCl₃, 500.14 MHz):
δ = 0.44 (s, 9 H, SiMe₃), 6.4-7.5 (18 H_arom). MS (EI, 70 eV): m/z (%) = 472 (13), 471 (36), 470 (100) [all M+], 469 (39). C₂₈H₂₇OPSSi (470.64): calcd C 71.46, H 5.78; found C 71.52, H 5.62.
3e: From 1b and 2c, malodorous colorless oil, isolated by bulb-to-bulb distillation at 80-100 °C/0.0001 mbar; 76% yield. IR (KBr): 1687 s, 1245 s, 1187 s, 841 s cm^-1. ¹H NMR (CDCl₃, 500.14 MHz): δ = 0.49 (d, ⁵ J _H,P = 1.5 Hz, 9 H, SiMe₃), 1.19 (dt, 6 H, CH₂CH ₃), 1.35 (m, 4 H, PCH₂), 1.86 (d, ⁵ J _H,P = 1.4 Hz, COCH₃), 6.90-7.00 (m, 2 H_Ph), 7.32-7.43 (m, 3 H_Ph). MS (EI, 70 eV): m/z (%) = 308 (2), 307 (9), 306 (43) [all M⁺], 217 (100). C₁₇H₂₇OPSi (306.46): calcd C 66.63, H 8.88; found C 67.31, H 8.25.

<A NAME="RG16702ST-8">8</A> Duncan M. Callagher MJ. Org. Magn. Reson. 1981, 15: 37

Crystal data for 3b: Triclinic, space group P1, a = 9.432 (3), b = 9.611 (2), c = 12.548 (3) Å, α = 98.82 (3), β = 102.21 (3), γ = 101.69 (3); Z = 2, D _calc = 1.149 g·cm^-3. Crystallographic data have been deposited at the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-187712. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax: +44(1223)336033).

Yield of crude 4a,b: ˜90%; since both compounds are extremely malodorous oils, we refrained from further purification. Data for 4a: ¹H NMR (CDCl₃, 500.14 MHz): δ = 0.17 (s, SiMe₃), 5.33 (d, ² J _H,P = 1.2 Hz, HCC≡C), 7.23-7.70 (m, 5 H_Ph). ¹³C{¹H} NMR (CDCl₃, 50.32 MHz): δ = 0.2 (s, SiMe₃), 64.4 (s, HCC≡C), 88.21 (d, J _C,P = 10.6 Hz) and 88.63 (d, J _C,P = 5.0 Hz) (C≡C). This product was isolated as a 6.2:1 mixture (³¹P NMR) with 5a [δ(¹H) = 0.43 (d, ⁵ J _H,P = 1.5, SiMe₃); δ(¹³C) = 1.8 (d, ⁴ J _C,P = 9.1, SiMe₃), 198.0 (³ J _C,P = 17.4, CHO); δ(³¹P) = 3.4].
Data for 4b: IR (film): 1679 m, 1599 m, 1251 vs, 1065 vs, 868 vs, 844 vs, 754 m cm^-1. ¹H NMR (CDCl₃, 200.13 MHz): δ = 0.16 (s, 9 H, SiMe₃), 0.90-1.15 (dt, 6 H, CH₂CH ₃), 1.30-1.70 (m, 4 H, PCH₂), 4.78 (d, J _H,P = 5.0 Hz, HCC≡C), 7.15-7.40 (m, 5 H_Ph). ¹³C{¹H} NMR (CDCl₃, 50.32 MHz): δ = 0.09 (s, SiMe₃), 9.85 and 9.95 (each d, J _C,P = 15.1 Hz, CH₂CH₃), 16.4 (d, J _C,P = 15.1 Hz, PCH₂), 16.7 (d, J _C,P = 14.1 Hz, PCH₂), 61.9 (d, J _C,P = 11.6 Hz, HCC≡C), 87.2 (s) and 87.9 (d, J _C,P = 4.0 Hz) (C≡C). This product was isolated as a 94:6 mixture (³¹P NMR) with 5b [δ(¹H) = 0.32 (d, ⁵ J _H,P = 1.6 Hz, SiMe₃); δ(¹³C) = 2.3 (d, ⁴ J _C,P = 10.7 Hz, SiMe₃)].

Allene 6 was obtained as an oil (˜97% purity by ³¹P NMR) which could not be purified further by chromatography or vacuum distillation without decomposition. ¹H NMR (CDCl₃, 500.14 MHz): δ = 0.21 (s, 9 H, SiMe₃), 1.04 and 1.42 (each dt, 3 H, PCH₂CH₃), 1.58-1.74 (m, 4 H, PCH₂), 7.24-7.38 (m, 6 H_Ph), 7.61 (dd, 2 H_Ph), 7.64 (dd, 2H_Ph).

7: colorless crystals, mp 89 °C. IR (KBr): 1688 (s, C=O), 1266 m, 1158 (s, P=O) cm^-1. ¹H NMR (CDCl₃, 400.13 MHz): δ = 1.01 (dt, ³ J _P,H = 17.0 Hz, ³ J _H,H = 7.7 Hz, 3 H, CH₂CH ₃), 1.23 (dt, ³ J _P,H = 17.2 Hz, ³ J _H,H = 7.7 Hz, 3 H, CH₂CH ₃), 1.49-1.74 (m, 2 H, PCH₂), 1.84-2.05 (m, 2 H, PCH₂), 3.80 (m_c, 2 H, COCH₂), 3.95 (m_c, 1 H, PCH), 7.26-7.55 (m, 8 H_arom), 7.96 (dd, 2 H_arom). ¹³C{¹H} NMR (CDCl₃, 100.61 MHz): δ = 5.88/5.92 (2 d, J _P,C = 44.3/44.3 Hz, PCH₂ CH₃), 18.51/19.25 (2 overlapping d, PCH₂), 38.6 (s, COCH₂), 39.1 (d, J _P,C = 61.4 Hz, CHPOEt₂), 127.2-137.5 (C_Ph), 196.9 (d, J _P,C = 10.2 Hz, CO). ³¹P (CDCl₃): δ = 54.8. C₁₉H₂₃O₂P (314.36): calcd C 72.59, H 7.37; found C 72.82, H 7.51.

For other methods to prepare γ-ketophosphinates and -phosphanoxides, see:

<A NAME="RG16702ST-14A">14a</A> Bell A. Davidson AH. Earnshaw C. Norrish HK. Torr RS. Trowbridge DB. Warren S. J. Chem. Soc., Perkin Trans. 1 1983, 2879

<A NAME="RG16702ST-14B">14b</A> Pudovik AN. Sovanov AA. Bakhtiyarova IV. Zimin MG. Zh. Obshch. Khim. 1983, 53: 2456

(Z)-8: Colorless oil. IR(film): 1669 (s, C=O), 1225 (s), 1174 (s, P=O) cm^-1. ¹H NMR (CDCl₃, 400.13 MHz): δ = 1.14 (dt, ³ J _P,H = 17.4 Hz, ³ J _H,H = 7.7 Hz, 6 H, PCH₂CH ₃), 1.80-1.97 (m, 4 H, POCH₂), 7.24 (d, ³ J _P,H = 30.5 Hz, 1 H, COCH=), 7.35-7.60 (3 m, 8 H_arom), 7.97-8.00 (dd, 2 H_arom). ¹³C{¹H} NMR (CDCl₃, 100.61 MHz): δ = 5.67 (d, J _P,C = 5.3 Hz, PCH₂ CH₃), 21.9 (d, J _P,C = 69.1 Hz, PCH₂), 128.1-128.8 (several C), 133.8 (CH), 137.0, 138.8 (d, J _P,C = 9.1 Hz), 142.3 (J _P,C = 5.4 Hz, COCH=), 145.8, 146.5, 192.9 (d, J _P,C = 4.9 Hz, C=O). ³¹P: δ = 46.4. C₁₉H₂₁O₂P (312.35): calcd C 73.06, H 6.78; found C 72.68, H 6.94. (E)-8: Colorless crystals, mp 80 °C. IR (solid, ATR): 1659 (s, C=O), 1254 (s), 1188 (s, P=O) cm^-1. ¹H NMR (CDCl₃, 400.13 MHz): δ = 1.25 (dt, ³ J _P,H = 16.9 Hz, ³ J _H,H = 7.6 Hz, 6 H, PCH₂CH ₃), 1.67-1.86 (m, 4 H, POCH₂), 7.09-7.52 (4 m, 8 H_arom), 7.82 (d, ³ J _P,H = 17.8 Hz, 1 H, COCH=), 7.87 (dd, 2 H_arom). ¹³C{¹H} NMR (CDCl₃, 100.61 MHz): δ = 5.42 (d, J _P,C = 5.7 Hz, PCH₂ CH₃), 19.6 (d, J _P,C = 69.8 Hz, PCH₂), 127.6-128.9 (several C), 133.5 (CH), 134.9 (d, J _P,C = 9.1 Hz), 136.6, 140.3 (J _P,C = 5.7 Hz, COCH=), 145.8, 146.5, 191.9 (d, J _P,C = 14.8 Hz, C=O). ³¹P: δ = 44.2. C₁₉H₂₁O₂P (312.35): calcd C 73.06, H 6.78; found C 73.11, H 6.83.