Prev. Article Next Article Table of Contents

Article

Ene-diamine versus Imine-amine Isomeric Preferences

Supporting Info

B. Jesse E. Reich, Erin E. Greenwald, Aaron K. Justice, Brittany T. Beckstead, Joseph H. Reibenspies, Simon W. North, and Stephen A. Miller*

Texas A&M University, College Station, Texas 77843-3255

J. Org. Chem., 2005, 70 (21), pp 8409–8416

DOI: 10.1021/jo051102g

Publication Date (Web): September 9, 2005

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

, samiller@mail.chem.tamu.edu

Abstract

Cyanide-catalyzed aldimine coupling was employed to synthesize compounds with 1,2-ene-diamine and α-imine-amine structural motifs: 1,2,N,N‘-tetraphenyletheylene-1,2-diamine (13) and (±)-2,3-di-(2-hydroxyphenyl)-1,2-dihydroquinoxaline (17), respectively. Single-crystal X-ray diffraction provided solid-state structures and density functional theory calculations were used to probe isomeric preferences within this and the related hydroxy-ketone/ene-diol system. The ene-diamine and imine-amine core structures were calculated (B3LYP/6-311++G(d,p)) to be essentially identical in energy (ΔG = 0.2 kcal/mol in favor of the imine-amine, within the error of the calculation). However, additional effectssuch as π conjugationin 13 render an ene-diamine structure that is slightly more stable than the imine-amine tautomer (14) (ΔG = 0.2−0.7 kcal/mol, within the error of the calculation). In contrast, the intramolecular hydrogen bonding present in 17 significantly favors the imine-amine isomer over the ene-diamine tautomer (18) (ΔG = 7.2−8.9 kcal/mol). For both 13 and 17, the optimized calculated structures (B3LYP/6-31+G(d‘)) are identical to those observed by single-crystal X-ray diffraction.

View: Full Text HTML | Hi-Res PDF

Tools

SciFinder Links

History

Published In Issue October 14, 2005
Received June 1, 2005

Recommend & Share

Related Content

Reductive Amination of Aldehydes and Ketones with Sodium Triacetoxyborohydride. Studies on Direct and Indirect Reductive Amination Procedures¹The Journal of Organic Chemistry
- Reductive Amination of Aldehydes and Ketones with Sodium Triacetoxyborohydride. Studies on Direct and Indirect Reductive Amination Procedures¹
  Ahmed F. Abdel-Magid, Kenneth G. Carson, Bruce D. Harris, Cynthia A. Maryanoff, and Rekha D. Shah
  The Journal of Organic Chemistry 1996 61 (11), pp 3849–3862
  Abstract: Sodium triacetoxyborohydride is presented as a general reducing agent for the reductive amination of aldehydes and ketones. Procedures for using this mild and selective reagent have been developed for a wide variety of substrates. The scope of the ...
  Abstract | Full Text HTML | Hi-Res PDF
Comparison of the Electronic Structures of Imine and Hydrazone Side-Chain Functionalities with the Aid of ¹³C and ¹⁵N NMR Chemical Shifts and PM3 Calculations. The Influence of CN-Substitution on the Sensitivity to Aromatic SubstitutionThe Journal of Organic Chemistry
- Comparison of the Electronic Structures of Imine and Hydrazone Side-Chain Functionalities with the Aid of ¹³C and ¹⁵N NMR Chemical Shifts and PM3 Calculations. The Influence of CN-Substitution on the Sensitivity to Aromatic Substitution
  K. Neuvonen, F. Fülöp, H. Neuvonen, A. Koch, E. Kleinpeter, and K. Pihlaja
  The Journal of Organic Chemistry 2003 68 (6), pp 2151–2160
  Abstract: Benzaldehyde derivatives possessing a CN double bond in the side-chain of the aromatic ring exhibit a reverse dependence of the ¹³C NMR chemical shifts of the CN carbon on the benzylidenic substituents X. Thus, electron-withdrawing substituents cause ...
  Abstract | Full Text HTML | Hi-Res PDF
Design of Brønsted Acid-Assisted Chiral Brønsted Acid Catalyst Bearing a Bis(triflyl)methyl Group for a Mannich-Type ReactionOrganic Letters
- Design of Brønsted Acid-Assisted Chiral Brønsted Acid Catalyst Bearing a Bis(triflyl)methyl Group for a Mannich-Type Reaction
  Aiko Hasegawa, Yuki Naganawa, Makoto Fushimi, Kazuaki Ishihara, and Hisashi Yamamoto
  Organic Letters 2006 8 (15), pp 3175–3178
  Abstract: A new Brønsted acid-assisted chiral Brønsted (chiral BBA) acid catalyst (1) was developed by substituting a hydroxy group of optically active 1,1‘-bi(2-naphthol) with a stronger Brønsted acidic group such as a bis(trifluoromethanesulfonyl)methyl group. ...
  Abstract | Full Text HTML | Hi-Res PDF

Article

Ene-diamine versus Imine-amine Isomeric Preferences