钯和铂促进的3,4-二甲基-1-苯基膦烯分子内[4 + 2]狄尔斯-阿尔德环加成反应的协同非对映选择性

Cooperative diastereoselectivity of palladium- and platinum-promoted intramolecular [4 + 2] Diels-Alder cycloaddition reactions of 3,4-dimethyl-1-phenylphosphole.

作者信息

Redwine K D, Wilson W L, Moses D G, Catalano V J, Nelson J H

机构信息

Department of Chemistry/216, University of Nevada-Reno, Reno, Nevada 89557-0020, USA.

出版信息

Inorg Chem. 2000 Jul 24;39(15):3392-402. doi: 10.1021/ic990885j.

DOI:10.1021/ic990885j

PMID:11196880

Abstract

The complexes [(DMPP)2M(CH3CN2)]X2 (DMPP = 3,4-dimethyl-1-phenylphosphole; M = Pd, Pt; X = BF4-, NO3-, ClO4-) react with 2 equiv of the dienophiles N,N-dimethylacrylamide (DMAA), 2-vinylpyridine (VyPy), and diphenylvinylphosphine (DPVP) to form bis-[4 + 2] Diels-Alder cycloaddition products. The [M(DMPP)2(DMAA)2]2+ and [M(DMPP)2(VyPy)2]2+ complexes form exclusively as the cis-geometric isomers, whereas for [M(DMPP)2(DPVP)2]2+, both cis- and trans-geometric isomers are formed. The two Diels-Alder cycloadditions occur sequentially, and the absolute configuration of the first reaction influences the absolute configuration of the second. In all cases, recemic mixtures of the (R,R) and (S,S) diastereomers are formed; none of the meso (R,S) diastereomer is observed. New complexes were characterized by elemental analyses, physical properties, infrared spectroscopy, 1H, 1H(31P), 13C(1H), and 31P(1H) NMR spectroscopy, and, in most cases, X-ray crystallography.

摘要

配合物[(DMPP)2M(CH3CN2)]X2（DMPP = 3,4 - 二甲基 - 1 - 苯基膦；M = Pd，Pt；X = BF4-，NO3-，ClO4-）与两当量的亲双烯体N，N - 二甲基丙烯酰胺（DMAA）、2 - 乙烯基吡啶（VyPy）和二苯基乙烯基膦（DPVP）反应，形成双[4 + 2]狄尔斯 - 阿尔德环加成产物。[M(DMPP)2(DMAA)2]2+和[M(DMPP)2(VyPy)2]2+配合物仅以顺式几何异构体形式形成，而对于[M(DMPP)2(DPVP)2]2+，顺式和反式几何异构体均有形成。两次狄尔斯 - 阿尔德环加成反应依次发生，第一次反应的绝对构型影响第二次反应的绝对构型。在所有情况下，均形成（R，R）和（S，S）非对映异构体的外消旋混合物；未观察到内消旋（R，S）非对映异构体。通过元素分析、物理性质、红外光谱、1H、1H(31P)、13C(1H)和31P(1H)核磁共振光谱对新配合物进行了表征，并且在大多数情况下还通过X射线晶体学进行了表征。