VI. Metal alkyls from oxidative addition / insertion
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1 V. Metal alkyls from oxidative addition / insertion A. Carbonylation - C insertion very facile, metal acyls easily cleaved, all substrates which undergo oxidative addition can in principle be carbonylated. 1. General Scheme (0) ox. add. C u cleave uc () C () () C insert 'M transmetallate (M = Sn, Zn, etc.) C ' + M red. el. C '
2 2. Examples Tf Tet. Lett. 29, 2793 (1988) (Ac) 2 cat PPh 3, Et 3 C, Me/DMF C 2 Me 75% Me C 2 Me (Ac) 2, L Me C 2 Me Tf C, DMF Et 3, Me 93% C 2 Me J. rg. Chem. 55, 3004 (1990) MM Tol Tf BM (Ac) 2 C Me DMF MM Tol BM Me Tol Tol 83% [Edstrom J. rg. Chem. 59, 6902 (1994); J. rg. Chem. 60, 5069 (1995)]
3 L 4 C SnBu % U92 = Ph,, Et, TMS [JACS 117, 8474 (1995)] [Boronic Acids TM Miyaura JC 63, 4726 (1998)] Ar (0)/C/Bu 3 Sn ArC C =, Br, Tf high yields (28 cases) Stille, J. Am. Chem. Soc. 108, 452 (1986) ntramolecular versions very popular. C 3 C 3 + C Cl 2 (PPh 3 ) 2 K 2 C 3, DMF 4 atm 50, 60 h C 3 C 3 78% J. Am. Chem. Soc. 102, 4193 (1980) J. rg. Chem. 47, 3630 (1982)
4 U92a C TPS TPS SAc Bu 3 Sn/C 2 dba 3,L TPS TPS SAc good yield A.B. Smith JACS, 123, 5925 (2001)
5 Ph Br Bn (Ac) 2 /PPh 3 Bu 3 /MPA 1 atm C, 100 Ph Bn 76% Y. Ban Chem. Comm. 698 (1979) Tetrahedron 41, 387 (1985) works well on large scale Br C, DMF L 2 Cl 2 ibu 3 J. rg. Chem. 52, 2469 (1987) (1994) and tbu 89% on 180 g scale S F 6.7 kg (Ac) 2 34 g Me 2.6 Kg DMS 73 l dppe 63 g C 7 psi Et kg Me 2 C 5.31 kg 87% [J. rg. Chem. 59, 6683 (1994)]
6 Even enolate can trap σ acyl L 2 Cl 2 /TF Et 3, psi C egishi, Tet. Lett. 31, 2941 (1990) 80-90% (B) lefin insertion - eck eaction, rg. eact. 27, 345 (1982) eviews: de Meijere Angew. Chem. nt. Ed. 33, 2379 (1994) Z β-elim. red. elim. Z verman Pure Appl. Chem. 66, 1423 (1994) (0) () () Z ox. add. coord. (no β-) Z (Z =,, Ph, C, C 2, Me, Ac, Ac) less substituted favored in intermolecular reaction regiochemistry of intramolecular rx depends on ring size and strain in T.S. Catalysts: L 4, (dba) 2, Cl 2 L 2 + DBAL, (Ac) 2 + red. agent (C, C 2 =C 2, 3, 3 P, ) Modifications igh T [Spencer J. rganomet. Chem. 258, 101 (1983); 265, 323 (1984); 270, 115 (1984)]
7 solated, stable, o-palladated cat. with high T Ph 2 P Ac 2 [Beller Angew. Chem. nt. Ed. Engl. 34, 1844 (1995)] Tf T Ac 2 Ac 2 [Milstein JCS Chem. Comm. 357 (1999)] disputed [JCS Chem. Comm (2000)] metallic claimed Cl 2 [Pacheco rg. Lett. 2, 1826 (2000)] S Cl S S Cl 2 [Guram rg. Lett. 2, 1287 (2000)] Me Me P P 2 2 [Shibasaki Tet. Lett. 40, 7379 (1999)] 8.9 million T 400,000 T/hϖ S S [Eur. J. rg. Chem. 869 (2000)]
8 C 2 Et Me Me C 2 Me Me (Ac) 2 cat DMF, Bu 4 Cl KAc, 80, 6 h [Sundberg J. rg. Chem. 55, 6208 (1990)] C 2 Et Me C 2 Me 89% Me Me Mild conditions ( 4 ) [Jeffrey, Larock J. rganomet. Chem. 258, 101 (1983); 265, 323 (1984); 270, 115 (1984) Tet. Lett. 26, 2667 (1985); 29, 905 (1988) Synthesis 70 (1987); Chem. Comm (1984)] ole of halide [Amatore, Jutland JACS 113, 8375 (1991)] (Stabilizes ntermediates) Prevents β-el. [rganomet. 19, 775 (2000)] [L 2 Ph] + better than (Ac) 2 / otol 3 p Bull. Chem. Soc. Jpn (1995)]
9 Tf TBS TBS U96 L 4 K 2 C 3 Bn MeC 4Å Mol. Siev. 90 [Masters, Danishefski Angew. Chem. nt. Ed. 34, 1723 (1995); 34, 452 (1995); JACS 117, 5228 (1995)] 49% Taxol Bn C C Tf dppb KAc DMA 90% [verman Tet. Lett. 39, 4643; 4647 (1998)] 1 Br 2 dba 3 dppb Ag 3 P 4 DMA 79% 1 C [Trost Angew. Chem. nt. Ed. Engl. 38, 3662 (1999)] Aromatic and heteroaromatic systems insert Br Br (0) 60% [Scott rg. Lett. 2, 1427 (2000)] [See also Tet. Lett. 41, 285 (2000)] [Takenchi, Synthesis, 237 (2002)] Ts Boc (Ac) 2 Ag 2 C 3 PPh 3 100% Ts [Synthesis 549 (2000)]
10 Good for macrocycles with high dilution or solid support U97 Polymer (Ac) 2 Ph 3 P Bu 4 Cl DMF/ 2 /Et 3 Polymer [JACS 117, (1995)] Synthesis of DG libraries Tet., 57, 2293 (2001) [non polymer bound: Tetrahedron Lett. 36, 6555 (1995) 30-42%] 78% egiochemistry a function of conditions TBS TBS standard (0) ' "Jeffrey" TBS TBS TBS TBS ' ' 32-68% 70% [igby J. Am. Chem.Soc. 117, 7834 (1995); Tet. Lett. 38, 1057 (1997)]
11 Can induce asymmetry - [eview Shibasaki J. Synth. rg. Chem. Jpn. 52, 956 (1994); Tet. 53, 7371 (1997)] Me TMS (0) () BAP TMS 92% yield 90% ee [Tietz Angew. Chem. nt. Ed. 33, 1089 (1994); Synlett 597 (1995)] Tf Cl Cl (Ac) 2 K 2 C 3 () BAP 78% yield 95% ee [Shibasaki J. Am. Chem.Soc. 116, (1994)] Me Me Tf (Ac) 2 () BAP K 2 C 3 62% yield 95% ee [Shibasaki J. rg. Chem. 60, 4322 (1995)] 2 dba 3 L* DMA Ag 3 P 4 93% 89% ee L* = Me Me PPh 2 PPh 2 [Tetrahedron Asymmetry 11, 1919 (2000)] For L* = [ayashi et. 52, 195 (2000)] Ph 2 P
12 elated ydroacylation U98a h[()bap] + (±) Ph C ox. add. kinetic es. Ph 34% yield >95% ee + Ph C 54% yield 54% ee Ph h - insert h red. el. Ph Saemuni Tet., 57, 205 (2001); 1197 (2001) of Alkynes 1 Me h[() tol BAP] + 1 Me Me 2 (±) also Me % ee Et 60-70% conv. Me desymmetrization 91-95% yield 82-95% ee Fu JACS, 124, (2002) 123, (2001)
13 lefin insertion generates a new M-C σ bond. f β-elimination can be suppressed, all of the known chemistry of M-C's can be utilized for additional reactions e.g. cascade polycyclizations - egedus, Trost, egishi, Larock, Grigg, etc. e.g. C insertion 5% Cl 2 (PPh 3 ) 2 Me/C 3 C/Ph ( ) n Et 3 40 atm C ( )n 100 ox. add. C C 2 Me olefin Me - ( ) n C insert ( ) n insert ( ) n insert ( ) n (low C pressure) red. elim. egishi, J. rg. Chem. 53, 915 (1988) ( ) n 75%
14 Polyene insertions [eview verman Pure Appl. Chem. 64, 1813 (1992) [eumann Tet. 52, 9289 (1996); 56, 5959 (2000)] [egishi Chem. ev. 96, 365 (1996)] [Malacria Chem. ev. 96, 289 (1996)] [Grigg Comprehensive rganometallic Chemistry 12, 299 (1995)] (0) 86% [verman J. Am. Chem. Soc. 110, 2328 (1988)] E E E = C 2 Et 3% (PPh 3 ) 4 Et 3 (2 equiv) MeC reflux, 12h [egishi J. Am. Chem. Soc. 112, 8590 (1990)] E E 76% 1 Br 2 2 (Ac) 2 Ag 2 C 3 PPh ox add 1) insert 2) β-el. J. rg. Chem. 1991, demeijer insert Eur. J. rg. Chem (1999) Angew. Chem. nt. Ed. Engl. 38, 1452 (1999)
15 S 2 Ph (0) S 2 Ph 70% [Grigg Tetrahedron Lett. 36, 8137 (1995)] [Many, many, many current examples] 3 Si (Ac) 2 Ph 3 P Ag 2 C 3 TBAF 82% [verman J. rg. Chem. 58, 5304 (1993)] [JACS 121, 5467 (1999)] Can induce asymmetry Tf 2 dba 3 L* 85% up to 91% ee L* = BAP [Keay Synlett 605 (1999)] L* = 7,7'-(Me) 2 BAP Tet. Asymmetry 11, 1919 (2000) Tf [TFA] 2 (S)-BAP C [ayashi rg. Lett. 1, 1487 (1999)] 95% ee
16 Can truncate by transmetallation Cl C 2 Me Sn C 2 Me Cl 2 (Tfp) 2 89% [da Tetrahedron 51, 695 (1995)] ucleophilic Attack Br C 2 Me C 2 Me 5% (Ac) 2 Me 2 C C2 Me dppe 1.1 K 76% [Balme Synlett 995; 998 (1998)]
o-palladated cat. [Chem. Comm (1999)] [Org. Lett. 2, 1826 (2000)] [Org. Lett. 2, 2881 (2000)] [JACS 41, 9550 (1999)]
![o-palladated cat. [Chem. Comm (1999)] [Org. Lett. 2, 1826 (2000)] [Org. Lett. 2, 2881 (2000)] [JACS 41, 9550 (1999)]](/thumbs/85/92754396.jpg "o-palladated cat. [Chem. Comm (1999)] [Org. Lett. 2, 1826 (2000)] [Org. Lett. 2, 2881 (2000)] [JACS 41, 9550 (1999)]")
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
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