第八周金属有机氢化反应及氢甲酰化反应摘要.ppt

* 过渡金属催化的反应 Turnover Turnover Frequency (TOF) Turnover Number (TON) Chemical selectivity Regio selectivity Stereo selectivity It has been clearly shown that PPh3 is readily lost due to steric crowding and that the inner catalyst cycle with a weakly coordinated solvent molecule (not shown) is about 1000 times faster than the outer cycle that has 3 PPh3 ligands coordinated to the metal. This hydrogenation catalyst is compatible with a variety of functional groups (ketones, esters, carboxylic acids, nitriles, nitro groups, and ethers) and indicates that the metal hydride intermediate is primarily covalent in character. Coordinatively unsaturated cationic catalysts that were considerably more active for hydrogenation were later discovered. The reason for this is that the cationic metal center is more electrophillic and this favors alkene coordination, which is often the rate determining reaction step. The ability to coordinate to the catalyst directly influences the rate of hydrogenation. Thus, unsaturated substrates containing polar functionality which can assist in binding to the catalyst have faster hydrogenation rates. Terminal alkynes are hydrogenated as well and at a faster rate than terminal alkenes (better binding and insertion). The following is the general trend in hydrogenation rates: 选择性： 氢化反应首先发生在最活泼的多重键。空间跟电子效应有重要的影响。 Directing Effects 定位效应 Amide OH OR ester ~ ketone Asymmetric Hydrogenation 95% of all hydrogenations use heterogeneous catalysts like Pd on carbon (Pd/C) or Raney Nickel. One area where homogeneous catalysis rules is asymmetric hydrogenation. This involves the use of a chiral catalyst and an alkene substrate that generates a chiral carbon center on hydrogenation. 这个氢化反应的机理与其他单齿配体配合物的不同。首先发生的是单体的配位而不是氢气的氧化加成。氧化加成是限速步骤。更为重要的是烯烃配位的异构体配合物（主要产物）通过X-射线表征，给出的是一种错误的信息。Halpern 证明了，那种次要异构体的反应速度比主要异构体的反应速度快580倍。 Ru 是一种很强的异裂活化氢气的催化剂。这种催化剂主要发生的是氢气的异裂而不是氧化加成。氢气与金属的配位削弱了H-H键的强度。 整个过程中Ru价态保持不变。 Tobin Marks reported the extraordinary activity of