o-palladated cat. [Chem. Comm (1999)] [Org. Lett. 2, 1826 (2000)] [Org. Lett. 2, 2881 (2000)] [JACS 41, 9550 (1999)]
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1 3. Boron -- eview [Suzuki Chem. ev. 95, 2457 (1995)] U77b ydroboration also attractive but B Pd transmetallation difficult - must produce stable B product - solved (by Suzuki) by adding base to make Borates which are stable! ote: F also promotes reaction [JC 59, 6095 (1994)] Desirable because boronic acids are stable, B by-products nontoxic Many new catalyst systems for Suzuki (also for Stille, etc.) PVP Pd nanoparticles [rg. ett. 2, 2385 (2000)] PdCl 2 /intercalated Clay [Tet. ett. 40, 439 (1999)] Pd(0)/ionic liquids [Chem. Comm (2000)] o-palladated cat. [Chem. Comm (1999)] [rg. ett. 2, 1826 (2000)] [rg. ett. 2, 2881 (2000)] [JACS 41, 9550 (1999)] For ArCl [JACS 122, 4020 (2000)] [Tet. ett. 40, 3855 (1999)] [JC 64, 3805 (1999)] [JC 64, 6797 (1999)] [Tet. ett. 41, 595 (2000)] eview ArCl & all TM and eck Fu Angew. Chem. nt. Ed., 41, 4176 (2002) i cat [Tet. 56, 2139 (2000)] [Tet. 55, (1999)] [Tet. ett. 40, 2323 (1999)] Solventless [rg. ett. 1, 1423 (1999)] Microwave/aqueous [JC 64, 3885 (1999)] To generate libraries [JACS 121, 9073 (1999)] [Tet. 55, (1999)]
2 ( ) n X n = 1, B 1 = tbu, Et, Ph, nbu, 2 = Pd(Ac) 2 aac ( ) n % Bull. Chem. Soc. Jpn. 60, 3471 (1987) Spectacular use Z-C () 2 B Tl Pd(0) 75 Y Y Y % Kishi, J. Am. Chem. Soc. 109, 4756 (1987)
3 C TBS Pd(0) C B(BB) [alcomb rg. ett. 2, 2687 (2000)] X (only 16%) B tbu B 4 Pd Base Ar ArX Pd(0) tbu [Satoh Tet. ett. 40, 213 (1999)] 10 cases good yields MM B(BB) Bn TBS Bn [rg. ett. 1, 1075 (1999)] (Ph) 2 P MM Bn Bn Bn 4 Pd TBS Bn Bn Bn
4 2 C BC Br () 2 B Cbz MEM Pd 2 dba 3 otol 3 P 90% [Boger JACS 121, 1004 (1999)] 2 C BC Cbz MEM B B [rg. ett. 2, 37 (2000)] Pd(0) couple on Channel-forming Tf (BB)BC 2 (C 2 ) 14 C C 3 [Fürstner JC 63, 3072 (1998)] (C 2 ) 15 CC 3
5 (White, J. rg. Chem., 66, 5217 (2001) U78c TBS C B TBS TBS PdCl 2 (C) 2 Ph 3 As Ag 2 TBS 70% Suzuki Suzuki Stille Sauvage, Tet. ett., 42, 2779 (2001)
6 Snieckus combined o-lithiation/boronation with Pd transmetallation Chem. ev. 90, 879 (1990) 1) i/b() 3 2) B() 2 Ar 1 Br Pd(0) a 2 C 3 Tet. ett. 28, 5093; 5097 (1987) Ar 1 1) i/b() 3 2) () 2 B Ar 1 Ar 2 Br Ar 2 Ar 1 Pd(0)/a 2 C 3 = C (ipr) 2 C Et 2 C tbu B() 2 Br C 2 Et Pd(PPh 3 ) 4 TF/rfx a 2 C 3 Tet. ett. 29, 2135 (1988) C 2 Et 82%
7 B C 2 (ipr) 2 2 [Snieckus JC 60, 292 (1995)] 4 Pd a 61% 2 CiPr 2 Br (C 2 ) 11 B() 2 4 Pd aq a 2 C 3 PhC 3 /Et (C 2 ) 11 AB 2 Building Blocks for iquid Crystal Dendrimers [Percec JACS 117, (1995)] () 2 B BC BC B() 2 Br Br Pd dba 2 Ph 3 P DME a 2 C 3 BC BC 60-80% n CF 3 C = nbu, nc 12, (C 2 ) 10 n [Tour JACS 116, (1994)]
8 4) Transmetallation from Sn, Si ArCl [Angew. Chem. nt. Ed. 38, 2411 (1999)] 0.5% Pd/C, 10% Cu, 20% AsPh 3 *ptimization of Stille coupling [Farina Tet. ett. 36, 2191 (1995)]; [Farina rg. eact., 50, 1 (1997)] CuCl accellerates sterically hindered substrates [Corey JACS 121, 7600 (1999)] Because of the very wide range of tin compounds available, and their stability, and their facile transmetallation to Pd, these are most useful in synthesis. ntramolecular review [Pattenden JCS Perkin Trans 1253 (1999)] ate and ease of transfer to Pd. Stille, Angew. Chem. nt. Ed. Engl. 25, 508 (1986) C C- > C=C > Ar >, ~ArC 2 >> C n 2n1 Vinyls transfer with retention of geometry allyls transfer with allylic transposition Any substrate that oxidatively adds to Pd(0) can be alkylated by 3 Sn' eg. acid halides J. Am. Chem. Soc. 104, 5808 (1982) Cl 4 Sn cat. BnPd(PPh 3 ) 2 Cl MPA 65 82% * 3 Si Cl Bu 3 Sn C 2 Bn 4 Pd CCl 3 65 * 3 Si 71% C 2 Bn J. rg. Chem. 48, 4634 (1983) J. Am. Chem. Soc. 109, 669 (1983)
9
10 TBS C 3 Sn S 2 PdCl 2 (C) 2 DMP C [Kende JACS 117, 8258 (1995)] TBS TPS S 2 TES TBS TBS Bu 3 Sn P 3 2 PdCl 2 DMF / TF 65% TPS [Smith JACS (1995)] TES TBS TBS
11 TBS TBS ( 3 Sn) 2 4 Pd tbu 2 C Sn 3 TBS TBS TBS PdCl 2 (C) 2 DMF ("ligandless Stille") [Panek JC 63, 4572 (1998)] tbu 2 C TBS TBS TBS TBS TBS Br Bu 3 Sn SnBu 3 2 PdCl 2 DBA 59%
12 Bu 3 Sn 2 1) Pd 2 dba 3 AsPh 3 (62%) double Stille 2) SnBu 3 Bu 3 Sn 2 45%
13 Bu 3 Sn U83b_ (1) 2 1) Pd 2 dba 3 double Stille (2) AsPh 3 (62%) 2) SnBu 3 Stille catalytic in Tin (Maleczka, JACS, 123, 3194 (2001) 1 x 6% 3 SnCl 1% 2 PdCl 2 1% Pd 2 dba 3 4% (fur) 3 P PMS (Si) 1 Pd() Sn 3 X 3 Sn Pd() 1 3 Snx ScX "Sc"
14 Stille coupling is effective for aryl-aryl and heteroaryl coupling J.J. i, G.W. Gribble "Palladium in eterocyclic Chemistry" Tet. rg. Chem. Series Vol. 20, Pergamon, 2000 Extensively used in materials chemistry (Tour, Frechet, Moore) Cl SnBu 3 Cl DMF Cl 2 PdCl 2 45% 2 PdCl 2 Bu 3 Sn SnBu 3 helical 31% [ehn JCS Chem. Comm. 765 (1995)] Br S S C 8 S 2 S S 3 Sn S Sn 3 ' 2 PdCl 2 dend S dend 65% 17 [Frechet JACS (2000)]
15 Aryl, vinyl triflates from phenols and ketones are good substrates. U84a_ Some require icl to react [Stille, JACS 109, 5478 (1987)] others are retarded by icl [Piers, JC 51, 3405 (1986)] icl effect depends on solvent, substrate, [Farina, JACS 113, 9585 (1991); JC 59, 5434 (1993)] Complex ch. [(Farina, Espinet), (Jutland, Amatore) Acta Chim. Scand. 52, 100 (1998); Acct. Chem. es. 33, 314 (2000); JACS 115, 9531 (1993); rganomet. 14, 1810 (1995) icl accelerates when ox. add. is slow (rate limiting) ( in 4 Pd weak donor such as Ph 3 As), retards in solvents of moderate polarity when transmetallation is rate limiting [Espinet, JACS 122, (2000)] 1 2 ' 2 Pd Cl Pd n ' 'Tf ' Pd Tf ote! Transmetallation can go with rentention or inversion at. C Sn Pd 1 Pd X cyclic, retention [ n-1 PdCl] Tf Pd or Cl Tf 2 SnBu 3 2 Pd 1 Pd Y C inversion S ' Pd S S 2 SnBu 3 SnBu 3 Tf
16 ots of examples U84b ychnovsky, Angew Chem. nt. Ed., 40, 3224 (2001) TMS P CEt 2 Bu 3 Sn Pd() Ph 3 As Couple 77% Bn Bn Tf 3 Sn Bn Bn 4 Pd cat. 2 eq. CuCl 2 eq. K 2 C 3 Bn Bn 81% Bn Bn [icolaou Angew. Chem. nt. Ed. Engl. 39, 887 (1996)]
17 TBS Tf Bu 3 Sn Ac 4 Pd icl 50% TBS [Danishefsky, JACS 121, 6563 (1999)] Ac FS 3 Fluorosulfonates also couple [oth JC 56, 3493 (1991) Alkynl iodides also couple 3 Si Ac Ac 3 Sn Sn 3 4 Pd cat. Si 3 3 Si Ac Ac [Danishefsky JC 59, 3755 (1994); Angew. Chem. nt. Ed. 33, 2477 (1994)] Si 3 80%
18
19 TE: Fluorosulfonates ( FS 3 also work.) oth, J. rg. Chem. 56, 3493 (1991) iyama in "tal Catalyzed Cross-Coupling eactions," (Diederich, Stang, Eds.) Wiley-VC, 1998 pp orn Chem. ev. 95, 1317 (1995) From Si (iyama) eview Syn. ett. 845 (1991). Si needs activation. X 'Si 3 2% PdCl/2 cat MPA or TF/P(Et) eq TASF ' 60-90% X = Ar, Br Br, ArTf, Tf ' = Ph ypervalent siloxanes also react [DeShong JC 64, 1684 (1999)] ArSi() 3 Si() 3 Si() 3 Ar'X Pd(dba) 2 TBAF DMF couple Via Si Ar F Bu 4
VI. Metal alkyls from oxidative addition / insertion
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