Role of ligands in controlling the regioselectivity in ruthenium-catalysed addition of carboxylic acids to terminal alkynes: A DFT study
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- 作者：BHOLANATH MAITY ; TOTAN MONDAL ; KAUSTAV DEY…
- 关键词：Enol esters ; DFT ; regio ; selectivity ; ligands ; ruthenium(II) catalyst.
- 刊名：Journal of Chemical Sciences
- 出版年：2015
- 出版时间：February 2015
- 年：2015
- 卷：127
- 期：2
- 页码：281-293
- 全文大小：1,458 KB
- 参考文献：1. (a) Rozen S and Lerman O 1979 / J. Am. Chem. Soc. 101 2782; (b) Wexler A, Balchunis R J and Swenton J S 1975 / J. Chem. Soc., Chem. Commun. 15 601; (c) House H O 1972 / Modern synthetic reactions, 2 nd edn Menlo Park, CA: W A Benjamin 313. (d) Tsuji J, Minami I and Shimizu I 1983 / Tetrahedron Lett. 24 4713; (e) Schmitt G Warwel S, Homminga E and Meltzow W 1972 / Justus Liebigs Ann. Chem. 763 75
2. (a) Monthéard J P, Camps M, Seytre G, Guillet J and Dubois J C 1978 / Angew. Makromol. Chem. 72 45; (b) Seidel A, J?gers E and Bylsma F 1993 / Eur. Pat. 0574 725 A1
3. Rotem M and Shvo Y 1983 / Organometallics 2 1689
4. (a) Mitsudo T, Hori Y and Watanabe Y 1985 / J. Org. Chem. 50 1566 (b) Mitsudo T, Hori Y, Yamakawa Y and Watanabe Y 1987 / J. Org. Chem. 52 2230
5. (a) Doucet H, Hofer J, Bruneau C and Dixneuf P H 1993 / J. Chem. Soc., Chem. Commun. 10 850 (b) Doucet H, Martin-Vanca B, Bruneau C and Dixneuf P H 1995 / J. Org. Chem. 60 7247 (c) Doucet P, Derrien N, Kabouche Z, Bruneau C and Dixneuf P H 1997 / J. Organomet. Chem. 551 151 (d) Bruneau C and Dixneuf P H 1999 / Acc. Chem. Res. 32 311 and references therein
6. Bruneau C, Neveux-Duflos M and Dixneuf P H 1999 / Green Chem. 1 183
7. Goossen L J, Paetzold J and Koley D 2003 / Chem. Commun. 6 706
8. (a) Bruneau C and Dixneuf P H 2008 / Angew. Chem. Int. Ed. 47 8492 (b) Rigaut S, Touchard D and Dixneuf P H 2004 / Coord. Chem. Rev. 248 1585
9. Gaussian 09, Revision C.01, Frisch M J, Trucks G W, Schlegel H B, Scuseria G E, Robb M A, Cheeseman J R, Scalmani G, Barone V, Mennucci B, Petersson G A, Nakatsuji H, Caricato M, Li X, Hratchian H P, Izmaylov A F, Bloino J, Zheng G, Sonnenberg J L, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven, T, Montgomery Jr J A, Peralta J E, Ogliaro F, Bearpark M, Heyd J J, Brothers E, Kudin K N, Staroverov V N, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant J C, Iyengar S S, Tomasi J, Cossi M, Rega N, Millam J M, Klene M, Knox J E, Cross J B, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann R E, Yazyev O, Austin A J, Cammi R, Pomelli C, Ochterski J W, Martin R L, Morokuma K, Zakrzewski V G, Voth G A, Salvador P, Dannenberg J J, Dapprich, S, Daniels A D, Farkas ?, Foresman J B, Ortiz J V, Cioslowski J and Fox D J Gaussian, Inc., Wallingford CT, 2010
10. (a) Maseras F and Morokuma K 1995 / J. Comput. Chem. 16 1170 (b) Vrevenand T and Morokuma K 2000 / J. Comput.Chem. 21 1419
11. (a) Hay P J and Wadt W 1985 / J. Chem. Phys. 82 270 (b) Hay P J, and Wadt W 1985 / J. Chem. Phys. 82 284 (c) Hay P J and Wadt W 1985 / J. Chem. Phys. 82 299
12. Hehre W J, Radom L, Schleyer P v R and Pople J A 1986 / Ab initio molecular orbital theory (New York: Wiley)
13. Helgren T A and Lipscomb W N 1977 / Chem. Phys. Lett. 49 225
14. Marenich A V, Cramer C J and Truhlar D 2009 / J. Phys. Chem. B 113 6378
15. Reed A E, Curtiss L A and Weinhold F 1998 / Chem. Rev. 88 899
16. (a) Oliván M, Eisenstein O and Caulton K G 1997 / Organometallics 16 2227 (b) Oliván M, Clot E, Eisenstein O and Caulton K G 1998 / Organometallics 17 3091
17. Kostic N M and Fenske R F 1982 / Organometallics 1 974
18. Bruneau C and Dixneuf P H 2006 / Angew. Chem. 118 2232; / Angew. Chem. Int. Ed. 45 2176
19. Varela-Fernández A, González-Rodríguez C, Varela J A, Castedo L and Saá C 2009 / Org. Lett. 11 5350
20. Wakatsuki Y, Koga N, Yamazaki H and Morokuma K 1994 / J. Am. Chem. Soc. 116 8105
21. Tokunaga M, Suzuki T, Koga N, Fukushima T, Horiuchi A and Wakatsuki Y 2001 / J. Am. Chem. Soc. 123 11917
22. (a) H?hn A, Otto H, Dziallas M and Werner H 19 - 刊物类别：Chemistry and Materials Science
- 刊物主题：Chemistry
Chemistry - 出版者：Springer India
- ISSN：0973-7103
文摘
Density functional studies are performed to understand the role of chelating bi-phosphine ligands [(Ph 2P(CH 2) m PPh 2); m = 1-] in modulating the regio-selectivity of benzoic acid addition to 1-hexyne, in presence of ruthenium(II) catalyst [(Ph 2P(CH 2)mPPh 2)Ru(methallyl) 2]. The Markovnikov addition to 1-hexyne is observed when catalyst 1 a [(Ph 2P(CH 2)PPh 2)Ru(methallyl) 2] is employed, whereas a reverse regio-selectivity is witnessed in presence of 1 d [(Ph 2P(CH 2)4PPh 2)Ru(methallyl) 2]. Anti-Markovnikov addition occurs via the neutral vinylidene intermediates (5 a / d ) formed after 1,2-hydrogen shift in hexyne coordinated ruthenium(II) complexes 3 a / d . The energy profile shows clear preference for Markovnikov addition by 15.0 kcal/mol ( \({\Delta } G_{\mathrm {L}}^{S})\) in case of catalyst system 1 a . In contrast, anti-Markovnikov pathway following neutral vinylidenes are more favourable by 9.1 kcal/mol ( \({\Delta } G_{\mathrm {L}}^{S})\) for catalyst system 1 d . The Z-enol ester formation is more predominant in the anti-Markovnikov pathway since the activation barrier for this step requires less energy (5.9 kcal/mol, \({\Delta } G_{\mathrm {L}}^{S})\) than the one furnishing the E-product. The calculated results are in good agreement with the reported experimental findings. Graphical Abstract Preliminary DFT studies are performed to explore the mechanistic pathway of the benzoic acid addition to 1-hexyne in presence of Ru(II) catalyst. Our calculations emphasized on the understanding of the regio-selectivity controlled by the chelating bi-phosphine ligand present in catalysts. Markovnikov product formation is the lower energy pathway in case of least spacer group (CH2) whereas it is anti-Markovnikov product for the highest spacer group, {(CH2)4} in bi-phosphine ligands.