Abstract
A general, chlorophosphine-free procedure for the preparation of phosphonites, phosphinites and tertiary phosphines with at least one sterically demanding substituent has been developed. In this modular methodology, successive addition of stoichiometric amounts of carbanionic nucleophiles such as organyllithium reagents to P(OPh)3 at low temperatures leads to selective stepwise substitution of the phenoxide leaving groups. Biphenyl-2-yl, 9-anthryl, and N -arylpyrrol-2-yl nucleophiles have been successfully employed for the first substitution step. Due to the steric shielding, the phosphorus derivatives are sufficiently stable for conventional aqueous work-up. Due to their phenoxide groups, diphenyl phosphonites and phenyl phosphinites usually possess sufficiently high melting points for the isolation by crystallization.
Key words
biaryls - ligands - metalations - phosphorus - pyrroles
References 1 To whom inquiries about the reported crystal structure analyses should be addressed.
2 Beller M.
Bolm C. In
Transition Metals for Organic Synthesis
Wiley-VCH;
Weinheim:
2004.
3a Murphy PJ. In
Organophosphorus Reagents
Oxford University Press;
Oxford:
2004.
3b Quin LD. In
A Guide to Organophosphorus Chemistry
Wiley-Interscience;
New York:
2000.
4 Cornils B.
Herrmann WA.
Schlögl R.
Wong C.-H. In
Catalysis from A-Z
Wiley-VCH;
Weinheim:
2003.
5 Petrov KA.
Agafonov SV.
Pokatun VP.
Chizov VM.
Zhurn. Obs. Khim.
1987,
57:
299 ; Chem. Abstr.
1988,
108:
56207
6 Scifinder Scholar search 9/6/2005.
7 Eisenträger F.
Goethlich A.
Gruber I.
Heiss H.
Kiener CA.
Krueger C.
Ulrich NJ.
Rominger F.
Scherhag G.
Schultz M.
Straub BF.
Volland MAO.
Hofmann P.
New J. Chem.
2003,
27:
540
8 Aldrich Catalogue Germany/Austria 2005-2006.
9 Christmann U.
Vilar R.
Angew. Chem. Int. Ed.
2005,
44:
366 ; Angew. Chem. 2005 , 117 , 370
10 Zapata AJ.
Rondon AC.
Org. Prep. Proced. Int.
1995,
27:
567
11 Brill TB.
Chem. Rev.
1984,
84:
577
12a 3 : Wolfsberger W.
Schmidbaur H.
Synth. React. Inorg. Met. Org. Chem.
1974,
4:
149
12b 3 C6 H2 ]3 P: Wada M.
Higashizaki S.
J. Chem. Soc., Chem. Commun.
1984,
482
12c Wada M.
Higashizaki S.
Tsuboi A.
J. Chem. Res., Synop.
1985,
38
12d 3 : Sharp PR.
Organometallics
1984,
3:
1217
12e d
15 -PEt3 : Whitesides GM.
Hackett M.
Brainard RL.
Lavalleye JPPM.
Sowinski AF.
Izumi AN.
Moore SS.
Brown DW.
Staudt EM.
Organometallics
1985,
4:
1819
12f 3 : Gibson VC.
Graimann CE.
Hare PM.
Green MLH.
Bandy JA.
Grebenik PD.
Prout K.
J. Chem. Soc., Dalton Trans.
1985,
2025
12g d
9 -PMe3 : Wenzel TT.
Bergman RG.
J. Am. Chem. Soc.
1986,
108:
4856
12h Heuer L.
Bode UK.
Jones PG.
Schmutzler R.
Z. Naturforsch. B
1989,
44:
1082
12i 3 : Luetkens ML.
Sattelberger AP.
Murray HH.
Basil JD.
Fackler JP.
Inorg. Synth.
1989,
26:
7
12j Luetkens ML.
Sattelberger AP.
Murray HH.
Basil JD.
Fackler JP.
Inorg. Synth.
1990,
28:
305
12k Ishii A.
Takaki I.
Nakayama J.
Hoshino M.
Tetrahedron Lett.
1993,
34:
8255
12l Mizwicki MT.
Haddadian F.
Kimmerling TS.
Muehl BS.
Sheu B.-J.
Storhoff BN.
Huffman JC.
Organometallics
2001,
20:
963
12m d
15 -PPh3 : Wang Q.
Dereda D.
Huynh C.
Schlosser M.
Chem. Eur. J.
2003,
9:
570
12n 3 : Kornath A.
Neumann F.
Oberhammer H.
Inorg. Chem.
2003,
42:
2894
12o 2 H3 )3 : Monkowius U.
Nogai S.
Schmidbaur H.
Organometallics
2003,
22:
145
13 Maienza F.
Spindler F.
Thommen M.
Pugin B.
Malan C.
Mezzeti A.
J. Org. Chem.
2002,
67:
5239
14 Sander M.
Chem. Ber.
1962,
95:
473
15 Durán E.
Velasco D.
López-Calahorra F.
J. Chem. Soc., Perkin Trans. 1
2000,
591
16 Emrich R.
Jolly PW.
Synthesis
1993,
39
17 Guillaneux D.
Martiny L.
Kagan HB.
Coll. Czech. Chem. Commun.
2000,
65:
717
18 Farugia LJ.
J. Appl. Cryst.
1997,
30:
565
19a Tolman CA.
Chem. Rev.
1977,
77:
313
19b Brown TL.
Inorg. Chem.
1992,
31:
1286
20a Sasaki S.
Sutoh K.
Murakami F.
Yoshifuji M.
J. Am. Chem. Soc.
2002,
124:
14830
20b Boeré RT.
Zhang Y.
J. Organomet. Chem.
2005,
690:
2651
21 Persistence of Vision Ray Tracer software under POV-Ray license from http://www.povray.org.
22a Walker SD.
Barder TE.
Martinelli JR.
Buchwald SL.
Angew. Chem. Int. Ed.
2004,
43:
1871 ; Angew. Chem. 2004 , 116 , 1907
22b Barder TE.
Buchwald SL.
Org. Lett.
2004,
6:
2649
22c Milne JE.
Buchwald SL.
J. Am. Chem. Soc.
2004,
126:
13028
22d Barder TE.
Walker SD.
Martinelli JR.
Buchwald SL.
J. Am. Chem. Soc.
2005,
127:
4685
23 Krasovskiy A.
Straub BF.
Knochel P.
Angew. Chem.
2005,
in press . DOI: 10.1002/ange.200502220
24a Zapf A.
Jackstell R.
Rataboul F.
Riermeier T.
Monsees A.
Fuhrmann C.
Shaikh N.
Dingerdissen U.
Beller M.
Chem. Commun.
2004,
38
24b Rataboul F.
Zapf A.
Jackstell R.
Harkal S.
Riermeier T.
Monsees A.
Dingerdissen U.
Beller M.
Chem. Eur. J.
2004,
10:
2983
25 Black D. In
Science of Synthesis
Vol. 9:
Maas G.
Thieme Verlag;
Stuttgart:
2002.
p.441
26 Mikolajziyk M.
Omelanczuk J.
Perlikowska W.
Tetrahedron
1979,
35:
1531
27a Walden P.
Ber. Dtsch. Chem. Ges.
1893,
26:
210
27b Walden P.
Ber. Dtsch. Chem. Ges.
1895,
28:
1287
27c Walden P.
Ber. Dtsch. Chem. Ges.
1895,
28:
2766
27d Walden P.
Ber. Dtsch. Chem. Ges.
1896,
29:
133
27e Walden P.
Ber. Dtsch. Chem. Ges.
1899,
32:
1855
28a Bent HA.
J. Chem. Educ.
1960,
37:
616
28b Bent HA.
Chem. Rev.
1961,
61:
275
29 Van Wazer JR.
Callis CF.
Shoolery JN.
Jones RC.
J. Am. Chem. Soc.
1956,
78:
5715
30 Grim SO.
McFarlane W.
Davidoff EF.
J. Org. Chem.
1967,
32:
781
31 Grim SO.
Yankowsky AW.
Phosphorus Sulfur Relat. Elem.
1977,
3:
191
32 Grim SO.
McFarlane W.
Davidoff EF.
Marks TJ.
J. Phys. Chem.
1966,
70:
581
33 Lin H.-S.
Paquette LA.
Synth. Commun.
1994,
24:
2503
34 Leleu J.
Cahiers de Notes Documentaires
1975,
78:
119
35 Tashiro M.
Yamato T.
J. Org. Chem.
1979,
44:
3037
