Ma Shengming, Ren Hongjun, Wei Qi
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai 200032, People's Republic of China.
J Am Chem Soc. 2003 Apr 23;125(16):4817-30. doi: 10.1021/ja034039q.
A highly regio- and stereoselective halohydroxylation of 1,2-allenyl sulfoxides with X(+) and water was developed. The reaction shows E-stereoselectivity. In the iodohydroxylation reaction, I(2) was used to introduce the iodine atom. For bromohalohydroxylation, CuBr(2), NBS, or Br(2) can be used. When using I(2), NBS, or Br(2), the addition of LiOAc.2H(2)O is necessary for high yields of the halohydroxylation products. The chlorohydroxylation reaction was preformed by milling 1,2-allenyl sulfoxides and CuCl(2).2H(2)O with silica gel. Under the catalysis of a Pd(0) complex, the halohydroxylation products, that is, E-2-halo-1-phenylsulfinyl-1-alken-3-ols, can undergo Sonogashira, Suzuki, and Negishi cross-coupling reactions leading to Z-2-substituted-1-phenylsulfonyl-1-alken-3-ols. The C-S bond of the coupling product may undergo a further coupling reaction with organozincs under the catalysis of an Ni catalyst. Here, the presence of a hydroxyl group is important for a smooth coupling involving the C-S bond. Thus, optically active stereodefined multisubstituted allylic alcohols can be prepared by the reaction of the easily available optically active propargylic alcohols with sulfinyl chloride followed by E-halohydroxylation and a selective Pd- or Ni-coupling reaction.
开发了一种用X(+)和水对1,2-联烯基亚砜进行高度区域和立体选择性卤代羟基化的方法。该反应具有E-立体选择性。在碘代羟基化反应中，使用I(2)引入碘原子。对于溴代卤代羟基化反应，可以使用CuBr(2)、NBS或Br(2)。当使用I(2)、NBS或Br(2)时，添加LiOAc·2H(2)O对于卤代羟基化产物的高产率是必要的。氯代羟基化反应是通过将1,2-联烯基亚砜和CuCl(2)·2H(2)O与硅胶研磨进行的。在Pd(0)配合物的催化下，卤代羟基化产物，即E-2-卤代-1-苯基亚磺酰基-1-烯-3-醇，可以进行Sonogashira、Suzuki和Negishi交叉偶联反应，生成Z-2-取代-1-苯基磺酰基-1-烯-3-醇。偶联产物的C-S键在Ni催化剂的催化下可能与有机锌进一步发生偶联反应。在此，羟基的存在对于涉及C-S键的顺利偶联很重要。因此，通过易得的旋光性炔丙醇与亚硫酰氯反应，然后进行E-卤代羟基化和选择性Pd-或Ni-偶联反应，可以制备旋光性立体定义的多取代烯丙醇。
