References
<A NAME="RY01804ST-1A">1a</A>
Curran DP.
Pharm. News
2002,
9:
179
<A NAME="RY01804ST-1B">1b</A>
Zhang W.
Tetrahedron
2003,
59:
4475
<A NAME="RY01804ST-2">2</A>
Handbook of Fluorous Chemistry
Gladysz JA.
Curran DP.
Horvath I.
Wiley-VCH;
Weinheim:
2004. ; in press
<A NAME="RY01804ST-3A">3a</A>
Curran DP.
Synlett
2001,
1488
<A NAME="RY01804ST-3B">3b</A>
Curran DP.
In Handbook of Fluorous Chemistry
Gladysz JA.
Curran DP.
Horvath I.
Wiley-VCH;
Weinheim:
2004.
Chap. 7. in press
<A NAME="RY01804ST-3C">3c</A>
Curran DP.
In Handbook of Fluorous Chemistry
Gladysz JA.
Curran DP.
Horvath I.
Wiley-VCH;
Weinheim:
2004.
Chap. 8. in press
Representative recent references:
<A NAME="RY01804ST-4A">4a</A> Dienophiles:
Werner S.
Curran DP.
Org. Lett.
2003,
5:
3293
<A NAME="RY01804ST-4B">4b</A> FCBz groups:
Curran DP.
Amatore M.
Guthrie D.
Campbell M.
Go E.
Luo ZY.
J. Org. Chem.
2003,
68:
4643
<A NAME="RY01804ST-4C">4c</A> Tin reagents:
Bucher B.
Curran DP.
Tetrahedron Lett.
2000,
41:
9617
<A NAME="RY01804ST-4D">4d</A> FDEAD:
Dandapani S.
Curran DP.
Tetrahedron
2002,
58:
3855
<A NAME="RY01804ST-4E">4e</A> Ester:
Chen CHT.
Zhang W.
Org. Lett.
2003,
5:
1015
<A NAME="RY01804ST-4F">4f</A> Scavengers:
Zhang W.
Chen CHT.
Nagashima T.
Tetrahedron Lett.
2003,
44:
2065
<A NAME="RY01804ST-4G">4g</A> Acetals:
Read RW.
Zhang CT.
Tetrahedron Lett.
2003,
44:
7045
<A NAME="RY01804ST-5A">5a</A>
Gladysz JA. In Handbook of Fluorous Chemistry
Gladysz JA.
Curran DP.
Horvath I.
Wiley-VCH;
Weinheim:
2004.
Chap. 5. in press
<A NAME="RY01804ST-5B">5b</A>
Dobbs AP.
Kimberley MR.
J. Fluorine Chem.
2002,
118:
3
<A NAME="RY01804ST-5C">5c</A>
Barthel-Rosa LP.
Gladysz JA.
Coord. Chem. Rev.
1999,
192:
587
<A NAME="RY01804ST-5D">5d</A>
Horváth IT.
Acc. Chem. Res.
1998,
31:
641
<A NAME="RY01804ST-5E">5e</A>
deWolf E.
van Koten G.
Deelman BJ.
Chem. Soc. Rev.
1999,
28:
37
<A NAME="RY01804ST-5F">5f</A>
Hope EG.
Stuart AM.
J. Fluorine Chem.
1999,
100:
75
<A NAME="RY01804ST-6A">6a</A>
Zhang Q.
Luo Z.
Curran DP.
J. Org. Chem.
2000,
65:
8866
<A NAME="RY01804ST-6B">6b</A>
Vallin KSA.
Zhang QS.
Larhed M.
Curran DP.
Hallberg A.
J. Org. Chem.
2003,
68:
6639
<A NAME="RY01804ST-7">7</A>
Croxtall B.
Hope EG.
Stuart AM.
Chem. Commun.
2003,
2430
For work on heavy fluorous palladium complexes, see:
<A NAME="RY01804ST-8A">8a</A>
Betzemeier B.
Knochel P.
Angew. Chem., Int. Ed. Engl.
1997,
36:
2623
<A NAME="RY01804ST-8B">8b</A>
Betzemeier B.
Lhermitte F.
Knochel P.
Tetrahedron Lett.
1998,
39:
6667
<A NAME="RY01804ST-8C">8c</A>
Shezad N.
Oakes RS.
Clifford AA.
Rayner CM.
Tetrahedron Lett.
1999,
40:
2221
<A NAME="RY01804ST-8D">8d</A>
Kling R.
Sinou D.
Pozzi G.
Choplin A.
Quignard F.
Busch S.
Kainz S.
Koch D.
Leitner W.
Tetrahedron Lett.
1998,
39:
9439
<A NAME="RY01804ST-8E">8e</A>
Moineau J.
Pozzi G.
Quici S.
Sinou D.
Tetrahedron Lett.
1999,
40:
7683
<A NAME="RY01804ST-8F">8f</A>
Chechik V.
Crooks RM.
J. Am. Chem. Soc.
2000,
122:
1243
<A NAME="RY01804ST-8G">8g</A>
Schneider S.
Bannwarth W.
Angew. Chem. Int. Ed.
2000,
39:
4142
<A NAME="RY01804ST-8H">8h</A>
Nishimura T.
Maeda Y.
Kakiuchi N.
Uemura S.
J. Chem. Soc., Perkin Trans. 1
2000,
4301
<A NAME="RY01804ST-8I">8i</A>
Schneider S.
Bannwarth W.
Helv. Chim. Acta
2001,
84:
735
<A NAME="RY01804ST-8J">8j</A>
Moreno-Mañas M.
Pleixats R.
Villarroya S.
Organometallics
2001,
20:
4524
<A NAME="RY01804ST-8K">8k</A>
Rocaboy C.
Gladysz JA.
Tetrahedron
2002,
58:
4007
<A NAME="RY01804ST-8L">8l</A>
Rocaboy C.
Gladysz JA.
Org. Lett.
2002,
4:
1993
<A NAME="RY01804ST-8M">8m</A>
Markert C.
Bannwarth W.
Helv. Chim. Acta
2002,
85:
1877
<A NAME="RY01804ST-8N">8n</A>
Rocaboy C.
Gladysz JA.
New J. Chem.
2003,
27:
39
<A NAME="RY01804ST-8O">8o</A>
Grigg R.
York M.
Tetrahedron Lett.
2000,
41:
7255
<A NAME="RY01804ST-9">9</A>
van der Boom ME.
Milstein D.
Chem. Rev.
2003,
103:
1759
<A NAME="RY01804ST-10A">10a</A>
Bergbreiter DE.
Osburn PL.
Liu YS.
J. Am. Chem. Soc.
1999,
121:
9531
<A NAME="RY01804ST-10B">10b</A>
Gruber AS.
Zim D.
Ebeling G.
Monteiro AL.
Dupont J.
Org. Lett.
2000,
2:
1287
<A NAME="RY01804ST-11A">11a</A>
This bromide, FluoroFlash silica gel and complex 3 are commercially available from Fluorous Technologies, Inc., www.fluorous.com.
<A NAME="RY01804ST-11B">11b</A>
DPC holds an equity interest in this company.
<A NAME="RY01804ST-12">12</A>
1H NMR (300 MHz, CDCl3): δ = 4.68 (s, 4 H, CH2), 7.08 (m, 4 H), 7.59 (d, 4 H, 3
J = 8.3 Hz), 7.93 (d, 4 H, 3
J = 8.3 Hz). 19F NMR (282.4 MHz, CDCl3): δ = -79.57 (m, 3 F, 3
J = 8.5 Hz), -109.86 (m, 2 F, CαF2), -120.32 (m, 4 F, CβF2, CδF2), -121.59 (m, 2 F, CεF2), -124.96 (m, 2 F, CγF2). 13C NMR (75 MHz, CDCl3): δ = 50.32 (CH2), 122.79, 125.59, 128.33, 130.23, 130.68, 136.75, 149.04, 161.84. EIMS: m/z = 1100 (M+), 1063 (M - Cl), 958 (M - PdCl), 513 (M - C8F17 - PdCl), 428 (HSPhC6F13). LCMS (APCl, neg. mode):
m/z = 1037, 957 (M - HPdCl), 427 (M - SPhC6F13). MS (APCl, pos. mode): m/z = 1063 (M - Cl).
<A NAME="RY01804ST-13">13</A>
Complex 3 crystallizes in space group P21/n with three crystallographically independent but chemically similar molecules per
asymmetric unit. The metric symmetry is suggestive of orthorhombic, with β equal to
90.02 (2)° but the crystal packing does not show any symmetry higher than monoclinic.
Each molecule consists of a Pd atom coordinated to a tridentate 1,3-bis(thiomethyl)benzene
SCS ligand with a Pd-Cl bond trans to the Pd-C bond. The environment about Pd is slightly distorted square planar. Distortions
are caused by the rigid SCS ligand, which results in non-linear S-Pd-S angles of 171.07
(7)°, 170.11 (7)° and 167.40 (7)° in the three independent molecules of 3. Pd-Cl bonds average 2.391 (2) Å, Pd-S bonds average 2.302 (2) Å, and Pd-C bonds
average 1.977 (8) Å. All three molecules have similar, well resolved Pd(SCS)Cl cores,
but differ in the orientation of the fluoroalkylaryl groups attached to S. For all
molecules, the two fluoroalkylaryl groups are on opposite sides of the Pd(SCS)Cl plane.
Differences lie in the twisting of the aryl rings. In two of the three molecules,
one of the fluoroalkyl chains is highly disordered and some fluorines and carbons
at the ends of these chains cannot be resolved.
<A NAME="RY01804ST-14A">14a</A>
Larhed M.
Moberg C.
Hallberg A.
Acc. Chem. Res.
2002,
35:
717
<A NAME="RY01804ST-14B">14b</A>
Olofsson K.
Kim SY.
Larhed M.
Curran DP.
Hallberg A.
J. Org. Chem.
1999,
64:
4539
<A NAME="RY01804ST-14C">14c</A>
Larhed M.
Hoshino M.
Hadida S.
Curran DP.
Hallberg A.
J. Org. Chem.
1997,
62:
5583
<A NAME="RY01804ST-15">15</A>
The recovered complex exhibited the same spectra as that starting complex and had
a bromine content of <0.15% by elemental analysis.
<A NAME="RY01804ST-16A">16a</A>
de Vries AHM.
Mulders JMCA.
Mommers JHM.
Hendricks HJW.
de Vries JG.
Org. Lett.
2003,
5:
3285
<A NAME="RY01804ST-16B">16b</A>
Consorti C.
Zanini ML.
Leal S.
Eberling G.
Dupont J.
Org. Lett.
2003,
5:
983
<A NAME="RY01804ST-16C">16c</A>
Nowotny M.
Hanefeld U.
van Konigsveld H.
Maschmeyer T.
Chem. Commun.
2000,
1877
