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	An Extensive Ylide Thermodynamic Stability Scale Predicted by First-Principle Calculations
	Fu, Yao ; Wang, Hua-Jing ; Chong, Sha-Sha ; Guo, Qing-Xiang ; Liu, Lei
	2010-10-12 ; 2010-10-12
关键词	DIMETHYL-SULFOXIDE SOLUTION C-H BONDS CONTINUUM SOLVATION MODELS EQUILIBRIUM ACIDITIES DISSOCIATION ENTHALPIES WITTIG REACTION AB-INITIO NEGATIVE HYPERCONJUGATION SULFONIUM YLIDES ORGANIC-ACIDS Chemistry, Organic
中文摘要	Thermodynamic stabilities of ylides are measured by the ease of the carbanion formation through the removal of a proton from their precursors. A full-spectrum scale of ylide thermodynamic stability is important to understand the reactivities and selectivities in ylide chemistry. In the present study is reported the first theoretical protocol for predicting the acidities of structurally unrelated ylide precursors in DMSO whose reliability has been tested against almost all the available experimental data. The ONIOM/G3B3// HF//CPCM/Bondi method is found to be the optimal protocol to handle the N-, P-, and S-containing ylides, whereas the B3LYP/6-311+G(3df,2p)//B3LYP/6-31G(d)//HF//CPCM/Bondi method can be used to deal with those systems for which the ONIOM/G3B3 method is not feasible. Extensive calculations on about 80 experimentally characterized ylide precursors show that this theoretical protocol can reliably predict the pK(a) values of diverse structurally unrelated ylide precursors in DMSO with an error bar of ca. 1.6-1.9 pK(a) units. With the authorized theoretical protocol in hand, we have developed an extensive scale of ylide thermodynamic stability that may find applications in synthetic organic chemistry.
语种	英语 ; 英语
出版者	AMER CHEMICAL SOC ; WASHINGTON ; 1155 16TH ST, NW, WASHINGTON, DC 20036 USA
内容类型	期刊论文
源URL	[http://hdl.handle.net/123456789/80923]
专题	清华大学
推荐引用方式 GB/T 7714	Fu, Yao,Wang, Hua-Jing,Chong, Sha-Sha,et al. An Extensive Ylide Thermodynamic Stability Scale Predicted by First-Principle Calculations[J],2010, 2010.
APA	Fu, Yao,Wang, Hua-Jing,Chong, Sha-Sha,Guo, Qing-Xiang,&Liu, Lei.(2010).An Extensive Ylide Thermodynamic Stability Scale Predicted by First-Principle Calculations..
MLA	Fu, Yao,et al."An Extensive Ylide Thermodynamic Stability Scale Predicted by First-Principle Calculations".(2010).

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