|
|
|
|
| LEADER |
01000caa a22002652 4500 |
| 001 |
NLM173588956 |
| 003 |
DE-627 |
| 005 |
20250208163319.0 |
| 007 |
cr uuu---uuuuu |
| 008 |
231223s2008 xx |||||o 00| ||eng c |
| 028 |
5 |
2 |
|a pubmed25n0579.xml
|
| 035 |
|
|
|a (DE-627)NLM173588956
|
| 035 |
|
|
|a (NLM)17849391
|
| 040 |
|
|
|a DE-627
|b ger
|c DE-627
|e rakwb
|
| 041 |
|
|
|a eng
|
| 100 |
1 |
|
|a Geng, Cai-Yun
|e verfasserin
|4 aut
|
| 245 |
1 |
0 |
|a Theoretical elucidation of the rhodium-catalyzed [4 + 2] annulation reactions
|
| 264 |
|
1 |
|c 2008
|
| 336 |
|
|
|a Text
|b txt
|2 rdacontent
|
| 337 |
|
|
|a ƒaComputermedien
|b c
|2 rdamedia
|
| 338 |
|
|
|a ƒa Online-Ressource
|b cr
|2 rdacarrier
|
| 500 |
|
|
|a Date Completed 11.06.2008
|
| 500 |
|
|
|a Date Revised 16.11.2017
|
| 500 |
|
|
|a published: Print
|
| 500 |
|
|
|a Citation Status MEDLINE
|
| 520 |
|
|
|a (c) 2007 Wiley Periodicals, Inc.
|
| 520 |
|
|
|a The reaction mechanism of the Rh-catalyzed [4 + 2] annulation of 4-alkynals with isocyanates is unraveled using density functional calculations. The reaction mechanisms of the model system and the real substituted system have been investigated and the results are compared. From our theoretical results based on the model and real substituted system, it is shown that (a) the rate-determining step is the Rh-H addition to the alkyne, (b) the formation of the cyclopentenone G and glutarimide K represents a severe competition, and (c) the product selectivity should be controlled by the amount of the isocyanates. In addition, it is demonstrated that there exist steric effects in the real substituted system, but missed in model system. Our calculations also show that although the results obtained on the model system could explain the mechanism in principle, the real substituted system could reflect the mechanism more exactly and make the reaction proceed with regioselectivity
|
| 650 |
|
4 |
|a Journal Article
|
| 650 |
|
7 |
|a Aldehydes
|2 NLM
|
| 650 |
|
7 |
|a Alkynes
|2 NLM
|
| 650 |
|
7 |
|a Cyclopentanes
|2 NLM
|
| 650 |
|
7 |
|a Isocyanates
|2 NLM
|
| 650 |
|
7 |
|a Ligands
|2 NLM
|
| 650 |
|
7 |
|a Piperidones
|2 NLM
|
| 650 |
|
7 |
|a Rhodium
|2 NLM
|
| 650 |
|
7 |
|a DMK383DSAC
|2 NLM
|
| 650 |
|
7 |
|a glutarimide
|2 NLM
|
| 650 |
|
7 |
|a MV728O9612
|2 NLM
|
| 650 |
|
7 |
|a cyclopentenone
|2 NLM
|
| 650 |
|
7 |
|a Q0U2IGF9CK
|2 NLM
|
| 700 |
1 |
|
|a Li, Ji-Lai
|e verfasserin
|4 aut
|
| 700 |
1 |
|
|a Huang, Xu-Ri
|e verfasserin
|4 aut
|
| 700 |
1 |
|
|a Liu, Hui-Ling
|e verfasserin
|4 aut
|
| 700 |
1 |
|
|a Li, Zhuo
|e verfasserin
|4 aut
|
| 700 |
1 |
|
|a Sun, Chia-Chung
|e verfasserin
|4 aut
|
| 773 |
0 |
8 |
|i Enthalten in
|t Journal of computational chemistry
|d 1984
|g 29(2008), 5 vom: 15. Apr., Seite 686-93
|w (DE-627)NLM098138448
|x 1096-987X
|7 nnns
|
| 773 |
1 |
8 |
|g volume:29
|g year:2008
|g number:5
|g day:15
|g month:04
|g pages:686-93
|
| 912 |
|
|
|a GBV_USEFLAG_A
|
| 912 |
|
|
|a SYSFLAG_A
|
| 912 |
|
|
|a GBV_NLM
|
| 912 |
|
|
|a GBV_ILN_350
|
| 951 |
|
|
|a AR
|
| 952 |
|
|
|d 29
|j 2008
|e 5
|b 15
|c 04
|h 686-93
|