Barry M. Trost 绿色化学领域的主要创始人、 原子经济性概念的提出者、 美国总统绿色化学挑战奖获得者 Ruthenium Catalyzed Reactions Lu-Trost-Inoue Reaction Tsuji-Trost Allylation Dinuclear Zinc Catalyst

Ruthenium Catalyzed Reactions

extreme conditions lack of selectivity limitations in terms of reaction partner Alder ene reaction In 1990s, this reaction is atom-economic but was found minimal use because of :

First Step

Ruthenium Catalysis: Mechanism Study

Chemoselectivity in the Ruthenium Catalyzed Redox Isomerization of Allyl Alcohols Trost, B.M.; Kulawiec, R.J. J. Am. Chem. Soc. (1993)

Barry M. Trost,* F. Dean Toste, and Hong Shen J. Am. Chem. Soc., 2000, 122 (10), pp 2379–2380

Paul A. Wender, J. Am. Chem. Soc., 1995, 117 (16), pp 4720–4721 Rh catalyzed 5+2 cycloaddition

Paul A. Wender,* J. Am. Chem. Soc., 1998, 120 (42), pp 10976–10977 Paul A. Wender, J. Am. Chem. Soc., 2006, 128 (19), pp 6302–6303

A Ruthenium-Catalyzed Hydrative Cyclization and [4 + 2] Cycloaddition of Yne-enones ?

(a) CpRu(CH 3 CN) 3 PF 6 (13 mol%), DCM, 34% (80% b.r.s.m.); (b) NBS, DMF, 98%; (c) CSA (10 mol%), CH 3 OH, 0 o C, 93–96%; Nature 456, (2008)

Ru catalysed yne-enone coupling/Michael addition Trost, B. M., Yang, H. & Wuitschik, G. A.. Org. Lett. 7, 4761–4764 (2005).

Tsuji-Trost Allylation

Lu-Trost-Inoue Reaction

Barry M. Trost, Thomas. Schmidt J. Am. Chem. Soc., 1988, 110 (7), pp 2301–2303 X. Lu, Tetraderon Lett. 1988, 29, 1045; Lu-Trost-Inoue ReactionTrost reported in 1992 that triphenylphosphine alone catalyzes the transformation when warmed to 80 – 110 o C in toluene B. M. Trost, J. Am. Chem. Soc. 1992, 114,7933; X. Lu, Chem. Commun. 1993, 394;

PPh3 and acetic acid were necessary to isomerize alkynyl esters, whereas PPh3 alone was sufficient to isomerize the more reactive alkynyl ketones.

Trost, B. M.; Li, C.-J. J. Am. Chem. Soc. 1994, 116, 3167.

Trost, B. M.; Dake, G. R. J. Org. Chem. 1997, 62, 5670.

Addition of Oxygen Nucleophiles to 2-Alkynoates

Jianwei Sun and Gregory C. Fu J. Am. Chem. Soc., 2010, 132 (13), pp 4568–4569 Ying Kit Chung, Gregory C. Fu, 8, 12, 9, 2009, Pages:

Dinuclear Zinc Catalyst

J. Am. Chem. Soc. 2006, 128, 8;