Prev. Article Next Article Table of Contents

Article

Polar Addition to C=C Group: Why Is Anti-Markovnikov Hydroboration–Oxidation of Alkenes Not "Anti-"?

Citing Articles

Your current credentials do not allow retrieval of the full text.

Purchase the full-text

PDF/HTML,
figures/images,
references and tables,
(where available)

Predrag-Peter Ilich , Lucas S. Rickertsen and Erienne Becker

Division of Molecular and Life Sciences, Loras College, Dubuque, IA 52001

J. Chem. Educ., 2006, 83 (11), p 1681

DOI: 10.1021/ed083p1681

Publication Date (Web): November 1, 2006

Section:

History, Education, and Documentation

Abstract

For 137 years Markovnikov's rule has been extensively used in organic chemical education and research to describe the regioselectivity in electrophilic addition reactions to alkenes and alkynes. When the structures of the final reaction products are used as reference, the rule requests that certain polar addition reactions be termed anti-Markovnikov. We use first principles thermodynamic calculations to analyze six polar addition reactions to alkenes, expected to be of either Markovnikov or anti-Markovnikov regioselectivity. Our results show no difference between the two reaction types: in each case the alkene atomic charges and the form of the intermediate completely determine the course of the overall reaction and the form of the predominant final product. We redefine this type of regioselectivity and propose that teaching of organic chemistry should be based more on robust and portable concepts such as energy difference and atomic charge than on historical labels.

Keywords (Audience):

Second-Year Undergraduate

Keywords (Domain):

Organic Chemistry

Keywords (Pedagogy):

Misconceptions / Discrepant Events

Keywords (Subject):

Addition Reactions

View: Hi-Res PDF | PDF w/ Links

Citing Articles

Citation data is made available by participants in CrossRef's Cited-by Linking service. For a more comprehensive list of citations to this article, users are encouraged to perform a search in SciFinder.

This article has been cited by 2 ACS Journal articles (2 most recent appear below).

Markovnikov's Rule
Predrag-Peter Ilich
Journal of Chemical Education2007 84 (7), 1109
- Markovnikov's Rule
  Predrag-Peter Ilich
  Journal of Chemical Education2007 84 (7), 1109
  More insight into the mechanisms of addition reactions to alkenes is needed before completely abandoning Markovnikov and anti-Markovnikov terminology
  Abstract | Hi-Res PDF | PDF w/ Links
Markovnikov's Rule
Robert C. Kerber
Journal of Chemical Education2007 84 (7), 1109
- Markovnikov's Rule
  Robert C. Kerber
  Journal of Chemical Education2007 84 (7), 1109
  The use of “Markovniknov” and “anti-Markovnikov” to describe addition reactions and their products has long outlived its utility.
  Abstract | Hi-Res PDF | PDF w/ Links