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 ReactionsRuthenium Catalyzed Reactions

Lu-Trost-Inoue Reaction

Tsuji-Trost AllylationTsuji-Trost Allylation

Dinuclear Zinc CatalystDinuclear Zinc Catalyst

Ruthenium Catalyzed ReactionsRuthenium 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 StepFirst 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) 115 2027

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

vinylcyclopropanesdiene-like

yne

diene 4+2

5+2

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

R Au

HO

?

(a) CpRu(CH3CN)3PF6 (13 mol%), DCM, 34% (80% b.r.s.m.);(b) NBS, DMF, 98%; (c) CSA (10 mol%), CH3OH, 0 oC, 93–96%; Nature 456,485-488(2008)

Ru catalysed yne-enone coupling/Michael addition

Trost, B. M., Yang, H. & Wuitschik, G. A..Org. Lett. 7, 4761–4764 (2005).

Tsuji-Trost AllylationTsuji-Trost Allylation

Lu-Trost-Inoue Reaction

Barry M. Trost, Thomas. SchmidtJ. Am. Chem. Soc., 1988, 110 (7), pp 2301–2303X. Lu, Tetraderon Lett. 1988, 29,1045;

Lu-Trost-Inoue Reaction Trost reported in 1992 that triphenylphosphine alone catalyzes the transformation when warmed to 80 – 110oC 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 reactivealkynyl 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. FuJ. Am. Chem. Soc., 2010, 132 (13), pp 4568–4569

Ying Kit Chung, Gregory C. Fu, 8, 12, 9, 2009, Pages: 2225-2227

Dinuclear Zinc CatalystDinuclear Zinc Catalyst

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