Computational prediction of regiospecificity in the [4+2] Diels-Alder cyclizations between the iminoborane (F 3C) 3C-B≡N-(t- Bu) and substituted cis-butadienes

Organometallics

Volumn 24, Issue 26, 2005, Pages 6445-6449

  Gilbert, Thomas M ^a  

^a NORTHERN ILLINOIS UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ELECTRON-DONATING GROUP; FRONTIER MOLECULAR ORBITALS (FMO); REGIOSPECIFICITY;

BORON; COMPUTATIONAL METHODS; NITROGEN; REACTION KINETICS;

ORGANOMETALLICS;

EID: 30344485121     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om050754s     Document Type: Article

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20. Transition states and products are labeled systematically in the text and Table 2 as follows. The first digit 2 indicates a transition state or product derived from 1. The substituent on the butadiene is given next. The following letter N means a structure in which the peripheral group on the added butadiene lies near the nitrogen atom of the iminoborane, while B means a structure in which the peripheral group lies near the boron atom. Transition states are labeled ts.
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23. 6)B=N(t-Bu) and cyclopentadiene occurs at low temperature. While the answer is not entirely certain as the requisite calculations and experiments have not yet been performed, the data in ref 6b indicate that cyclizations involving cyclopentadiene display lower barriers than those involving cis-butadiene, possibly due to decreased ring strain in the transition state for cyclizations involving the former.
24. N.
25. 2.
26. NBO charges are discussed here because they generally give more interpretable trends than do Mulliken charges. A useful discussion on this topic appears in: Bachrach, S. M. In Reviews in Computational Chemistry; Lipkowitz, K., Boyd, D. B., Eds.; VCH: New York, 1994; Vol. 5, Chapter 3. The trends in Mulliken charges from the G98 output mirror those for the NBO charges.
27. The literature regarding FMO theory is vast. Two papers of use in preparing this one were: (a) Hirao, H.; Ohwada, T. J. Phys. Chem. A 2005, 109, 816-824.
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