Dearomative Synthesis of Chiral Dienes Enables Improved Late-Stage Ligand Diversification
Dearomative Synthesis of Chiral Dienes Enables Improved Late-Stage Ligand Diversification
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DOI：
10.1021/acs.orglett.2c00183
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发表时间：
2022-03-11
期刊：
影响因子：
5.2
通讯作者：
Johnson, Jeffrey S.
中科院分区：
文献类型：
--
作者：
Crawford, Evan T.;Smith, Kendrick L.;Johnson, Jeffrey S.
通过苯甲醚的对映选择性分子间芳烃环丙烷反应，实现了手性非外消旋二烯配体的高效合成。生成的环庚三烯的官能团在下游的三环双(烯醇)三氟酸盐中产生了不同的化学环境，从而允许选择性的后期官能化。因此，通过钯催化的交叉偶联反应可以合成不同的C-1和准C-2对称双烯。这些配体在已知的Rh(I)介导的不对称转化中提供了中等到高的选择性。
An efficient synthesis of chiral nonracemic diene ligands is facilitated by an enantioselective dearomative intermolecular arene cyclopropanation of anisole. The functionality of the resulting cycloheptatriene engenders distinct chemical environments in a downstream tricyclic bis(enol) triflate that permits selective late-stage functionalization. The synthesis of diverse C-1- and pseudo-C-2-symmetric dienes is therefore viable by iterative palladium-catalyzed cross-coupling reactions. The ligands provide moderate to high selectivities in known Rh(I)-mediated asymmetric transformations.