Boron-enabled geometric isomerization of alkenes via selective energy-transfer catalysis

doi:10.1126/science.abb7235

GSTDTAP > 气候变化

DOI	10.1126/science.abb7235
	Boron-enabled geometric isomerization of alkenes via selective energy-transfer catalysis
	John J. Molloy; Michael Schäfer; Max Wienhold; Tobias Morack; Constantin G. Daniliuc; Ryan Gilmour
	2020-07-17
发表期刊	Science
出版年	2020
英文摘要	Compounds with carbon-carbon double bonds can form two distinct isomers, depending on whether the heaviest substituents on both carbons lie on the same side (labeled Z) or diagonally across from each other (labeled E). Molloy et al. present a convenient method to reorient double bonds that bear boron and carbonyl substituents. When they are diagonally opposed, both substituents stay in plane, and the double bond is easily swiveled by photosensitization. However, once on the same side as the carbonyl, the boron rotates out of plane and further sensitization is inhibited. Science this issue p. [302][1] Isomerization-based strategies to enable the stereodivergent construction of complex polyenes from geometrically defined alkene linchpins remain conspicuously underdeveloped. Mitigating the thermodynamic constraints inherent to isomerization is further frustrated by the considerations of atom efficiency in idealized low–molecular weight precursors. In this work, we report a general ambiphilic C3 scaffold that can be isomerized and bidirectionally extended. Predicated on highly efficient triplet energy transfer, the selective isomerization of β-borylacrylates is contingent on the participation of the boron p orbital in the substrate chromophore. Rotation of the C(sp2)–B bond by 90° in the product renders re-excitation inefficient and endows directionality. This subtle stereoelectronic gating mechanism enables the stereocontrolled syntheses of well-defined retinoic acid derivatives. [1]: /lookup/doi/10.1126/science.abb7235
领域	气候变化 ; 资源环境
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引用统计
文献类型	期刊论文
条目标识符	http://119.78.100.173/C666/handle/2XK7JSWQ/284350
专题	气候变化资源环境科学
推荐引用方式 GB/T 7714	John J. Molloy,Michael Schäfer,Max Wienhold,et al. Boron-enabled geometric isomerization of alkenes via selective energy-transfer catalysis[J]. Science,2020.
APA	John J. Molloy,Michael Schäfer,Max Wienhold,Tobias Morack,Constantin G. Daniliuc,&Ryan Gilmour.(2020).Boron-enabled geometric isomerization of alkenes via selective energy-transfer catalysis.Science.
MLA	John J. Molloy,et al."Boron-enabled geometric isomerization of alkenes via selective energy-transfer catalysis".Science (2020).