Rhenium-Catalyzed Synthesis of Multisubstituted Aromatic Compounds via C-C Single-Bond Cleavage
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1 henium-catalyzed Synthesis of Multisubstituted Aromatic Compounds via C-C Single-Bond Cleavage Kuninobu, Y.; Takata,.; Kawata, A.; Takai, K. rg. Lett. ASAP Et 5 6 cat. [ebr(c) 3 (thf)] Current Literature Kalyani Patil 6/28/08 Kalyani Wipf Group Page 1 of 13 7/3/2008
2 utline Synthesis of Substituted Aromatic Compounds henium Catalyzed eactions henium Catalyzed C- Activation - Takai Group Title Paper Summary Kalyani Wipf Group Page 2 of 13 7/3/2008
3 Synthesis of Substituted Aromatic Compounds Bergman cyclization C benzene cyclohexadiene Bergman et. al. J. Am. Chem. Soc. 1972, 94, 660 Trimerization of acetylenes (C 2 )n CpCo(C) % C 2 Vollhardt Angew. Chem. Int. Ed. 1984, 23, 539 ML x ML x-1 ML x-2 ML x xidative coupling to give metallacyclopentadiene Alkyne insertion or Diels-Alder type addition 5 ML x-2 4 ML x-2 6 ML x-2 Kalyani Wipf Group Page 3 of 13 7/3/2008
4 Synthesis of Substituted Aromatic Compounds ing-closing metathesis n-pr n-pr Grubbs' II C 2 Cl 2, rt, 2h n-pr n-pr n-pr n-pr Imamoto et. al. J. Am. Chem. Soc. 2005, 127, Annulation of vinylketenes with acetylenes C 3 benzene, 80 C, 26h 3 C 4 e - electrocyclic cleavage 6 e - electrocyclic closure Danheiser et. al. J.rg. Chem. 1984, 49, 1672 [22] 3 C 4 e - electrocyclic cleavage 3 C Kalyani Wipf Group Page 4 of 13 7/3/2008
5 Properties of henium Grayish white metal, last naturally occurring element to be discovered Discovered in 1925 by Dr. Walter Noddack and Dr. Ida Tacke Noddack Electronic configuration: [Xe] 4f14 5d5 6s2 xidation states: -3, -1, 0, 1 to 7 Lower electronegativity than u and h Kalyani Wipf Group Page 5 of 13 7/3/2008
6 henium Catalyzed eactions Friedel-Crafts alkylation ebr(c) t-bucl 5 (1 mol%) ClC 2 C 2 Cl, 84 C t-bu 93% C 3 C 3 Sonoda et. al. Bull. Chem. Soc. Jpn. 2000, 73, 2779 Anti-Markovnikov addition of carboxylic acids to terminal alkynes C ebr(c) 5 (1 mol%) toluene, 110 C 67% 13:87 ua et. al. J. rg. Chem. 2004, 69, 5782 Coupling of epoxides with C 2 C 2 ebr(c) 5 (0.1 mol%) 110 C, 85% ua et. al. J. rg. Chem. 2005, 70, 381 Kalyani Wipf Group Page 6 of 13 7/3/2008
7 henium Catalyzed eactions - Toste Group Etherification of propargylic alcohols n-bu 1 mol% (dppm)ecl 3 Cl MeCN, 65 C 78% Cl n-bu Toste et. al. J. Am. Chem. Soc. 2003, 125, 6076 X [M] -X [M] [3,3] [] [M] Synthesis of 1,5-Enynes TMS 5 mol% (dppm)ecl 3 cat. N 4 PF 6 MeN 2, 65 C 79% Toste et. al. J. Am. Chem. Soc. 2003, 125, Kalyani Wipf Group Page 7 of 13 7/3/2008
8 henium Catalyzed ing Expansion - Takai Group Construction of medium size rings Insertion of terminal alkynes into C-C next to the carbonyl group n Et [ebr(c) 3 (thf)] 2 (2.5 mol%) C 2 NC (5 mol%) Et neat, 24h Et 87% 78% 78% 61% n (4-b) Et Et Et (4-a) e (I) (3-b) Et henacyclopentene intermediate Et (2-b) e Et (2-a) etro-aldol reaction/isomerization eductive elimination e (3-a) e Et Et Takai et. al. J. Am. Chem. Soc.2006, 128, Kalyani Wipf Group Page 8 of 13 7/3/2008
9 henium Catalyzed C- Activation - Takai Group Formation of indene derivatives N t-bu Me cat. [ebr(c) 3(thf)] 2 toluene, reflux, 24h 95% N t-bu Takai et. al. J. Am. Chem. Soc. 2005, 127, C 2 Et cat. [ebr(c) 3 (thf)] 2 p-anisidine (15 mol%) toluene, 180 C, 24h 93% C 2 Et Takai et. al. Angew. Chem. Int. Ed. 2006, 45, 2766 Synthesis of isobenzofuran N cat. [ebr(c) 3 (thf)] 2 MS 4Å toluene, reflux, 24h 93% Takai et. al.j. Am. Chem. Soc. 2006, 128, Kalyani Wipf Group Page 9 of 13 7/3/2008
10 Title Paper Et [ebr(c) 3 (thf)] 2 (2.5 mol%) MS 4Å (200 wt%-e cat.) toluene, 180 C, 24h 5 6 toluene, 150 C, 24h 5 6 Entry 5 6 Yield (%) 1. Me Me C 2 Et C 2 Et Me C 2 Et C 2 Et Me C 2 Et C 2 Et Me Me Me C 2 Et C 2 Et Me Me C 2 Et C 2 Et Me Me n-c C 2 Et C 2 Et Me n-c 5 11 n-c 6 13 C 2 Et C 2 Et 85, A:B = 96:4 8. n-c 5 11 Me n-c 6 13 C 2 Et C 2 Et 83, A:B = 6:94 9. Me Me C 2 Et Me C 2 Et 77, C:D = 39:61 Et 2 C C 2 Et n-c 5 11 Et 2 C C 2 Et C 2 Et Et 2 C n-c 5 11 n-c 6 13 n-c 6 13 A B C D Kuninobu, Y.; Takata,.; Kawata, A.; Takai, K. rg. Lett. ASAP Kalyani Wipf Group Page 10 of 13 7/3/2008
11 DA w/ Benzyne Title Paper [ebr(c) 3 (thf)] 2 (2.5 mol%) MS 4Å (200 wt%-e cat) Et 1 eq. toluene, 180 C 1 (1eq.) Benzyne generated in situ to synthesize naphthalene derivatives SiMe 3, CsF(3 eq.) Tf (1.5 eq.) toluene/c 3 CN, 20 C, 12h 2 time (h) yield (%) Me (1a) (2a) (1b) (2b) Intramolecular eaction Et [ebr(c) 3 (thf)] 2 (2.5 mol%) MS 4Å (100 wt%-e cat) toluene, 150 C, 24h Synthesis of tetrahydronaphthalene derivatives Me 2 C C 2 Me (4 eq.) Me 2 C C 2 Me (84%) toluene, 150 C, 48h Kuninobu, Y.; Takata,.; Kawata, A.; Takai, K. rg. Lett. ASAP Kalyani Wipf Group Page 11 of 13 7/3/2008
12 Title Paper: Proposed Mechanism Et Et 5 6 (5) 5 6 (6) -C e (I) (1) henacyclopentene intermediate etro-aldol reaction/reductive elimination (4) -Et C 2 Et Et (3-b) 2 (2-b) (3-a) C 2 Et e (2-a) e C 2 Et Isomerization of the alkene/cyclization DA reaction/decarboxylation Kuninobu, Y.; Takata,.; Kawata, A.; Takai, K. rg. Lett. ASAP Kalyani Wipf Group Page 12 of 13 7/3/2008
13 Summary Synthesis of Multisubstituted Aromatic Compounds in Good Yields Products are btained in igh egioselectivity Aliphatic and Aromatic Acetylenes employed Prior to DA eaction Kalyani Wipf Group Page 13 of 13 7/3/2008
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