With a little help from my friends: Forty years of fruitful chemical collaborations

Journal of Organic Chemistry

Volumn 76, Issue 9, 2011, Pages 2943-2964

  Borden, Weston Thatcher ^a  

^a UNIVERSITY OF NORTH TEXAS   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

COLLABORATIVE RESEARCH; COPE REARRANGEMENT; CYCLOBUTANE RING; DIRADICALS; FLUORINE SUBSTITUTION; HUND'S RULE; ORGANIC REACTION; PHENYLNITRENES; THEORETICAL CHEMISTRY;

BUTANE; FLUORINE; OLEFINS; RESEARCH;

ORGANIC CARBON;

CARBENE; CYCLOBUTANE DERIVATIVE; HYDROCARBON;

CHEMICAL BOND; CHEMICAL INTERACTION; CHEMICAL STRUCTURE; CYCLIZATION; MOLECULE; ORGANIC CHEMISTRY; RESEARCH; REVIEW; THEORETICAL STUDY;

EID: 79955564973     PISSN: 00223263     EISSN: 15206904     Source Type: Journal    
DOI: 10.1021/jo200213x     Document Type: Review

References (255)

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19. For his doctoral research, Bill was working with E. J. Corey on developing a program to do computerized organic synthesis. However, Bill had also written a graphics program, to make the plots of MOs that appeared in The Organic Chemist's Book of Orbitals, (10) the book that Bill coauthored with Lionel Salem, who was at the time a visiting Professor at Harvard. The MOs that were plotted were generated by the EH program that Bill had written and which he used in the calculations for our collaboration.
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52. Professor Longuet-Higgins might have been the smartest person whom I have ever met, and he most definitely was the person who was least willing to suffer fools gladly. From the number of times he said to me in our weekly tutorial, "Weston, you are talking nonsense," I suspected that Professor Longuet-Higgins did not think that I had a bright future in theoretical chemistry. Many years later, I was reminded of both Professor Longuet-Higgins's blunt honesty as well as the low esteem in which he apparently held me by his reply to an email message I wrote to him, thanking him for helping me to learn electronic structure theory. I wrote that I was not sure that he would remember who I was, but he did; for he replied, "I remember you very well. You wrote that dreadful paper on the excited states of allene (Borden, W. T. J. Chem. Phys. 1966, 45, 2512), on which I refused to allow you to put my name."
53. Lionel had gotten his Ph.D degree with H. C. Longuet-Higgins; I had the impression that Professor Longuet-Higgins had a great deal of respect for Lionel's intellect, which was not the way I would describe Longuet-Higgins' feelings about mine. (29) In addition, in 1962, when I was a Freshman and Lionel was an Instructor at Harvard, I had been invited to a party at his house by my roommate, who was doing undergraduate research with Lionel. I was very impressed that James Watson and Francis Crick were, purportedly, also attending Lionel's party. However, as an 18 year-old Freshman, I was even more impressed that many of the guests were gorgeous French women, all of whom seemed to be very good friends of Lionel's.
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57. In fact, I had given this as a problem on an exam on PPP calculations in the course on MO theory that I taught at Harvard. However, until Lionel showed interest in this result, it did not occur to me that it might actually be worth publishing. Subsequently, I have become a little more confident that a result, which I find interesting and which has not been published by someone else, may actually turn out to be worth my publishing.
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60. This was also the lesson that I learned from the papers that Roald Hoffmann published in the late 1960s and early 1970s. Although it was well-known that the Extended Hückel (EH) method that Roald used was quantitatively unreliable, Roald provided such convincing qualitative explanations of his EH results that it always seemed to me Roald's EH results must be correct. Perhaps the tremendous increase in the accuracy of electronic structure calculations during the past 40 years has had the undesirable consequence that computational chemists feel less obliged to provide the kind of detailed physical explanations of their results than Roald routinely furnished 40 years ago.
61. Yarkony, D. R.; Schaefer, H. F., III. J. Am. Chem. Soc. 1974, 96, 3754
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67. Probably I had picked up some of the skepticism that my mentor, H. C. Longuet-Higgins, had about the use of "machine experiments" as a tool for understanding chemistry. See, for example: Jordan, P. H. C.; Longuet Higgins, H. C. Mol. Phys. 1962, 5, 121
68. Davidson, E. R.; Borden, W. T. J. Am. Chem. Soc. 1977, 99, 2053
69. I have to confess that, when I wrote the first draft of the paper, I was trying to impress Ernest and to convince him that his organic chemist collaborator knew enough theoretical chemistry to be an (almost) equal partner in our collaboration. I have described elsewhere some of the benefits that our very different backgrounds had for our collaboration, and I have also described some of the difficulties that these differences caused. [ Borden, W. T. Mol. Phys. (special issue in honor of Ernest Davidson), 2002, 100, 337.] For example, my drawing a hexagon with a circle in the middle of it was insufficient for Ernest to recognize that the molecule I had drawn as benzene. Ernest used to say, "If I do a calculation on benzene, I have to put in the hydrogens; so you should include them in your drawings too."
70. Borden, W. T.; Davidson, E. R. J. Am. Chem. Soc. 1977, 99, 4587
71. Soon after Ernest's and my paper appeared, I noticed that in his own papers Jerry Berson had begun calling NBMOs that have no atoms in common "disjoint". Since I thought this was an elegant term, in a phone conversation I asked Jerry for the reference to the first paper in which this term had been used. In a surprised tone of voice he replied, "You used the term 'disjoint' in the first line of the abstract of your paper with Davidson." I had, in fact, inserted this word into the abstract, just before I submitted the manuscript, and then I had totally forgotten that I had done so. I am grateful to Jerry for reintroducing me to this term and for helping to popularize its use.
72. ST in non-Kekulé hydrocarbons have been published: Borden, W. T. In Magnetic Properties of Organic Materials; Lahti, P. M., Ed.; Marcel Dekker: New York, 1999; pp 61-102.
73. Lineberger, W. C.; Borden, W. T. Phys. Chem., Chem. Phys. 2011, in press.
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76. Subsequently, using valence bond (VB) theory, Ovchinikov showed that, in general the spin quantum number, S, of the ground state of any AH can be predicted from S = (n *-n)/2, where n * and n are, respectively, the number of starred and unstarred atoms (Ovchinikov, A. A. Theor. Chim. Acta. 1978, 47, 297) The advantages and disadvantages of the MO and VB approaches for predicting the ground states of diradicals have been discussed. (49a)
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88. Rodriguez, E.; Reguero, M.; Caballol, R. J. Phys. Chem. A 2000, 104, 6253
89. Reviews: Borden, W. T.; Iwamura, H.; Berson, J. A. Acc. Chem. Res. 1994, 27, 109
90. Kutzelnigg, W. Angew. Chem., Int. Ed. Engl. 1996, 35, 573
91. Hrovat, D. A.; Borden, W. T. THEOCHEM 1997, 398, 211
92. Hrovat, D. A.; Borden, W. T. In Modern Electronic Structure Theory and Applications in Organic Chemistry; Davidson, E. R., Ed.; World Scientific Publishing Company: Singapore, 1997; pp 171-195.
93. Following the publication of my paper with Lionel, (36) every few months I would get a phone call from Jerry. He invariably began, "Hi, Wes, this is Jerry. Say, have you ever thought about...". These phone calls usually led to my group undertaking a new computational project on the subject of.... After Jerry retired and the phone calls from him stopped, I realized how much Jerry had contributed to my group's research on diradicals. Even though we only wound up publishing one paper (57a) and one review article (55a) together, next to Ernest, Jerry was really my closest senior collaborator.
94. Du, P.; Hrovat, D. A.; Borden, W. T.; Lahti, P. M.; Rossi, A. R.; Berson, J. A. J. Am. Chem. Soc. 1986, 108, 5072
95. Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1994, 116, 6327
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99. Reynolds, J. H.; Berson, J. A.; Scaiano, J. C.; Berinstain, A. B. J. Am. Chem. Soc. 1992, 114, 5866
100. Reynolds, J. H.; Berson, J. A.; Kumashiro, K. K.; Duchamp, J. C.; Zilm, K. W.; Scaiano, J. C.; Berinstain, A. B.; Rubello, A.; Vogel, P. J. Am. Chem. Soc. 1993, 115, 8073
101. Review: Borden, W. T.; Davidson, E. R. Acc. Chem. Res. 1996, 29, 67
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104. Review: Neumark, D. M. Acc. Chem. Res. 1993, 26, 33
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108. ̇- in solution.
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112. Wenthold, P. G.; Hrovat, D. A.; Borden, W. T.; Lineberger, W. C. Science 1996, 272, 1456
113. 8 h COT that it revealed. Consequently, when Carl and I quickly agreed on a version of a manuscript that described our next collaboration, (68) we were both greatly relieved. But then relief turned to dismay when we discovered that Carl and I had each created very different types of artwork to submit to Angew. Chem. as possible art for the cover. Fortunately, Carl's former post-doc, Takatoshi Ichino, sent us his own draft of cover art for our manuscript, and it was so good that Carl and I immediately discarded our drafts. Carl and I are both very grateful to Takatoshi, not only for his artwork, which did, in fact, appear on the cover of Angew. Chem., but also for saving Carl and me from having to work out a painful and time-consuming compromise between our first drafts of possible artwork for the cover.
114. In a more recent collaboration with Carl, on measuring the singlet-triplet energy separation in oxyallyl, the NIPE spectrum again had an unexpected feature. Very broad lines for all the peaks corresponding to the singlet but not the triplet state were observed. Ichino, T.; Villano, S. M.; Gianola, A. J.; Goebbert, D. J.; Velarde, L.; Sanov, A.; Blanksby, S. J.; Zhou, X.; Hrovat, D. A.; Borden, W. T.; Lineberger, W. C. Angew. Chem., Int. Ed. 2009, 48, 8509
115. Ichino, T.; Villano, S. M.; Gianola, A. J.; Goebbert, D. J.; Velarde, L.; Sanov, A.; Blanksby, S. J.; Zhou, X.; Hrovat, D. A.; Borden, W. T.; Lineberger, W. C. J. Phys.Chem. A 2011, in press. This provided the first clue that singlet oxyallyl is actually the transition structure for ring opening and ring closure of cyclopropanone. Despite singlet oxyallyl's being a transition structure, we were able to measure not only its energy, relative to that of the triplet, but also the C=O stretching frequency in the singlet. This is another good example of how useful NIPES can be for doing transition state spectroscopy. (62)
116. Review: Platz, M. S. Acc. Chem. Res. 1995, 28, 487
117. Kim, S.-J.; Hamilton, T. P.; Schaefer, H. F. J. Am. Chem. Soc. 1992, 114, 5349 For more recent calculations, see: Castell, O.; García, V. M.; Bo, C.; Caballol, R. J. Comput. Chem. 1996, 17, 42
118. Winkler, M. J. Phys. Chem. A 2008, 112, 8649
119. Karney, W. L.; Borden, W. T. J. Am. Chem. Soc. 1997, 119, 1378
120. Drzaic, P. S.; Brauman, J. I. J. Am. Chem. Soc. 1984, 106, 3443
121. Drzaic, P. S.; Brauman, J. I. J. Phys. Chem. 1984, 88, 5285
122. Matzinger, S.; Bally, T.; Patterson, E. V.; McMahon, R. J. J. Am. Chem. Soc. 1996, 118, 1535
123. Schreiner, P. R.; Karney, W. L.; Schleyer, P.v.R.; Borden, W. T.; Hamilton, T. P.; Schaeffer, H. F., III. J. Org. Chem. 1996, 61, 7030
124. Wong, M. W.; Wentrup, C. J. Org. Chem. 1996, 61, 7022
125. Zezsch, C.; Stuhl, F. Chem. Phys. Lett. 1975, 33, 375
126. Engelking, P. C.; Lineberger, W. C. J. Chem. Phys. 1976, 65, 4323
127. Travers, M. J.; Cowles, D. C.; Clifford, E. P.; Ellison, G. B. J. Chem. Phys. 1999, 111, 5349
128. ST in nitrenes and in methylene, as well as in non-Kekulé hydrocarbons and COT, have been reviewed recently. (49b)
129. Travers, M. J.; Cowles, D. C.; Clifford, E. P.; Ellison, G. B. J. Am. Chem. Soc. 1992, 114, 8699
130. McDonald, R. N.; Davidson, S. J. J. Am. Chem. Soc. 1993, 115, 10857
131. Wijeratne, N. R.; Da Fonte, M.; Ronemus, A.; Wyss, P. J.; Tahmassebi, D.; Wenthold, P. G. J. Phys. Chem. A 2009, 113, 9467
132. Reviews: Borden, W. T.; Gritsan, N. P.; Hadad, C. M.; Karney, W. L.; Kemnitz, C. R.; M. S. Platz, M. S. Acc. Chem. Res. 2000, 33, 765
133. Gritsan, N. P.; Platz, M. S.; Borden, W. T. In Theoretical Methods in Photochemistry; Kutateladze, A., Ed.; Taylor and Francis: Boca Raton, FL, 2005. See also
134. Karney, W. L.; Borden, W. T. In Advances in Carbene Chemistry; Brinker, U. H., Ed.; Elsevier: Amsterdam, 2001; Vol. 3, pp 206-251.
135. Karney, W. L.; Borden, W. T. J. Am. Chem. Soc. 1997, 119, 3347
136. Gritsan, N. P.; Gudmundsdottir, A. D.; Tigelaar, D.; Platz, M. S. J. Phys. Chem. A 1999, 103, 3458
137. Gritsan, N. P.; Tigelaar, D.; Platz, M. S. J. Phys. Chem. A. 1999, 103, 4465
138. Gritsan, N. P.; Likhotvorik, I.; Tsao, M.-L.; Çelebi, N.; Platz, M. S.; Karney, W. L; Kemnitz, C. R.; Borden, W. T. J. Am. Chem. Soc. 2001, 123, 1425
139. Tsao, M.-L.; Gritsan, N.; James, T. R.; Platz, M. S.; Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 2003, 125, 9343
140. Moss, R. A.; Ho, G.; Liu, W. J. Am. Chem. Soc. 1992, 114, 959
141. Albu, T. V.; Lynch, B. J.; Truhlar, D. G.; Moss, R. A.; Goren, A. C.; Hrovat, D. A.; Borden, W. T. J. Phys. Chem. A 2002, 106, 5323
142. Zuev, P.; Sheridan, R. S.; Albu, T. V.; Truhlar, D. H.; Hrovat, D. A.; Borden, W. T. Science 2003, 299, 867
143. While Don and I were polishing the manuscript for this Science paper, on several successive mornings at 1:30 AM in Seattle I found myself talking on the phone with Don, debating the best word to use in a particular sentence. Since 1:30 AM in Seattle is 3:30 AM in Minneapolis, I concluded that one reason for Don's incredible productivity is that he apparently needs very little or no sleep.
144. The first recognition of the importance of a very narrow barrier in facilitating tunneling by carbon appears to have been in: Carpenter, B. K. J. Am. Chem. Soc. 1983, 105, 1700
145. Shelton, G. R.; Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 2007, 129, 164
146. Shelton, G. R.; Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 2007, 129, 16115
147. Datta, A.; Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 2008, 130, 2726
148. Wu, A.; Mader, E. A; Datta, A.; Hrovat, D. A.; Borden, W. T.; Mayer, J. M. J. Am. Chem. Soc. 2009, 131, 11985
149. I owe the idea for this project to a previous collaboration with Karen Goldberg, a former colleague at UW, on the differences between the mechanisms for reductive elimination of methane from Pt(II) and Pt(IV) complexes. Bartlett, K. L.; Goldberg, K. I; Borden, W. T. J. Am. Chem. Soc. 2000, 122, 1456
150. Bartlett, K. L.; Goldberg, K. I; Borden, W. T. Organometallics 2001, 20, 2669
151. This project is one of several collaborations I have had with Jim Mayer, another former colleague at UW. I was very pleased that, even after I left UW, Jim continued to ask my group to do calculations to help interpret his group's experimental findings.
152. Datta, A.; Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 2008, 130, 6684
153. Zhang, X.; Datta, A.; Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 2009, 131, 16002
154. Zhang, X.; Datta, A.; Hrovat, D. A.; Borden, W. T. Org. Biomol. Chem. 2011, in press.
155. Zhang, X.; Hrovat, D. A.; Borden, W. T Org. Lett. 2010, 12, 2798
156. Sander, W. Unpublished results, communicated privately.
157. Gonzalez-James, O. M.; Zhang, X.; Datta, A.; Hrovat, D. A.; Borden, W. T.; Singleton, D. A. J. Am. Chem. Soc. 2010, 132, 12648
158. In discussing the role of tunneling in the 1,5-hydrogen shift in cis -1,3-pentadiene, Bill Doering wrote, "The tunneling effect [in this reaction] is likely, in the opinion of some, to remain relegated to the virtual world of calculation." (Doering, W.; Von, E.; Zhao, X. J. Am. Chem. Soc. 2006, 128, 9080) It certainly matters less to experimentalists than to theoretical chemists whether one type of calculation (e.g., CVT + SCT) fits experimental data better than another type of calculation (e.g., CVT). Since I think that Bill made a valid point in this intentionally provocative passage, all of my group's calculations on tunneling have sought to predict phenomena (e.g., curved Arrhenius plots, (87a, 87b) rapid reactions at cryogenic temperatures, (90a, 90d) and anomalous KIEs (87c, 87d, 90b)), which, if observed experimentally, would, by themselves, indicate the importance of tunneling in a reaction.
159. Doering, W. v. E.; Wang, Y. J. Am. Chem. Soc. 1999, 121, 10112
160. Dewar, M. J. S.; Wade, L. E. J. Am. Chem. Soc. 1973, 95, 290
161. Dewar, M. J. S.; Wade, L. E. J. Am. Chem. Soc. 1977, 99, 4417
162. Borden, W. T. Modern Molecular Orbital Theory for Organic Chemists; Prentice-Hall: Englewood Cliffs, NJ, 1975;, pp 129-132.
163. Woodward and Hoffmann used a very similar orbital correlation diagram to show that in the Cope TS the interaction between C-2 and C-5 of 1,5-pentadiene is antibonding. (5)
164. While living in Okazaki, I contracted an acute case of Nipponophilia, which caused me to attempt to learn to speak Japanese, to study ikebana (flower arranging) and chado (tea ceremony), and to compulsively return to Japan whenever I could. I continue to suffer from this now-chronic affliction.
165. Borden, W. T. In Theory and Applications of Computational Chemistry: The First 40 Years; Dykstra, C.; Frenking, G.; Kim, K.; Scuseria, G., Eds; Elsevier, Oxford, 2005; pp 859-872.
166. Osamura, Y.; Kato, S.; Morokuma, K.; Feller, D.; Davidson, E. R.; Borden, W. T. J. Am. Chem. Soc. 1984, 106, 3362
167. Morokuma, K.; Borden, W. T.; Hrovat, D. A. J. Am. Chem. Soc. 1988, 110, 4474
168. Dewar, M. J. S. J. Am. Chem. Soc. 1984, 106, 209
169. We made this claim in a review article titled, "Synchronicity in Multibond Reactions": Borden, W. T.; Loncharich, R. J.; Houk, K. N. Annu. Rev. Phys. Chem. 1988, 39, 213 Thanks to Ken, this review ended with an extended quote from the song "Synchronicity" by Sting. We claimed the existence of this song showed that the topic of synchronicity is of interest to more than just a small group of computational chemists. Members of the Houk group had T-shirts made with the words to the song "Synchronicity" emblazoned upon them
170. See, for example: Dewar, M. J. S.; Jie, C. J. Am. Chem. Soc. 1987, 109, 5893
171. Dewar, M. J. S.; Jie, C. J. Chem. Soc., Chem. Commun. 1987, 1451
172. Dupuis, M.; Murray, C.; Davidson, E. R. J. Am. Chem. Soc. 1991, 113, 9756
173. Doering, W. von E.; Toscano, V. G.; Beasley, G. H. Tetrahedron 1971, 27, 5299
174. Hrovat, D. A.; Morokuma, K.; Borden, W. T. J. Am. Chem. Soc. 1994, 116, 1072
175. Kozlowski, P. M.; Davidson, E. R. J. Chem. Phys. 1994, 100, 3672
176. Kozlowski, P. M.; Dupuis, M.; Davidson, E. R. J. Am. Chem. Soc. 1995, 117, 774
177. Ken Houk and I believe that Bill Doering did not really trust either of us to work on this problem and/or to obtain the correct answer. That is why we think Bill asked us each separately to do calculations on the effect of substituents on the Cope TS, without telling us that he had also asked the other. When Ken and I discovered at a Reaction Mechanisms Conference that Bill had gotten both of us to start work on this project, we decided to collaborate on completing it.
178. Wiest, O.; Black, K. A.; Houk, K. N. J. Am. Chem. Soc. 1994, 116, 10336
179. Jiao, H.; Schleyer, P. v. R. Angew. Chem., Int. Ed. Engl. 1995, 34, 334
180. Hrovat, D. A.; Beno, B. R.; Lange, H.; Yoo, H.-Y.; Houk, K. N.; Borden, W. T. J. Am. Chem. Soc. 1999, 121, 10529
181. Hrovat, D. A.; Chen, J.; Houk, K. N.; Borden, W. T. J. Am. Chem. Soc. 2000, 122, 7456
182. Roth, W. R.; Lennartz, H.-W; Doering, W. v. E.; Birladeanu, L.; Guyton, C. A.; Kitagawa, T. J. Am. Chem. Soc. 1990, 112, 1722
183. Doering, W. v. E.; Birladeanu, L.; Sarma, K.; Blaschke, G.; Scheidemantel, U.; Boese, R.; Benet-Bucholz, J.; Klärner, F.-G.; Gehrke, J.-S.; Zinny, B.-U.; Sustmann, R.; Korth, H.-G. J. Am. Chem. Soc. 2000, 122, 193
184. Doering, W. v. E.; Wang, Y. J. Am. Chem. Soc. 1999, 121, 10112
185. Hrovat, D. A.; Borden, W. T. J. Chem. Theory. Comput. 2005, 1, 87
186. Pyramidalized alkenes have been reviewed: Borden, W. T. Chem. Rev. 1989, 89, 1095
187. Luef, W.; Keese, R. In Topics in Stereochemistry; Eliel, E. L.; Wilen, S. H., Eds.; Wiley: New York, 1991; Vol. 20, pp 231-318.
188. Review: Borden, W. T. Synlett 1996, 711
189. Theophanous, F. A.; Tasiopoulous, A. J.; Nicolaides, A.; Zhou, X.; Johnson, W. T. G.; Borden, W. T. Org. Lett. 2006, 8, 3001
190. Eaton, P. E.; Maggini, M. J. Am. Chem. Soc. 1988, 110, 7230
191. Cubene was subsequently generated in the gas phase and its π BDE was measured. Staneke, P. O.; Ingemann, S.; Eaton, P.; Nibbering, N. M. M.; Kass, S. R. J. Am. Chem. Soc. 1994, 116, 6445
192. Hassenruck, K.; Radziszewski, J. G.; Balaji, V.; Murthy, G. S.; McKinley, A. J.; David, D. E.; Lynch, V. M.; Martin, H.-D.; Michl, J. J. Am. Chem. Soc. 1990, 112, 873
193. Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1990, 112, 875
194. Eaton, P. E.; Tsanaktsidis, J. J. Am. Chem. Soc. 1990, 112, 876
195. Eaton, P. E.; Yang, C.-X.; Xiong, Y. J. Am. Chem. Soc. 1990, 112, 3225
196. Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1990, 112, 3227
197. Moriarty, R. M.; Tuladhar, S. M.; Penmasta, R.; Awasthi, A. K. J. Am. Chem. Soc. 1990, 112, 3228
198. Eaton, P. E.; Zhou, J. P. J. Am. Chem. Soc. 1992, 114, 3118
199. Hrovat, D. A.; Borden, W. T.; Eaton, P. E.; Kahr, B. J. Am. Chem. Soc. 2001, 123, 1289
200. The calculations on cubane derivatives, suggested by Phil, (118b, 119b) led us to undertake two other computational projects involving cubyl derivatives. We provided explanations of why tert -butoxyl radical abstracts a cubyl, rather than a methyl hydrogen from methylcubane, even though the methyl C-H bond has a much lower BDE (Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1994, 116, 6459 and cubylcarbinyl radical undergoes rapid ring opening, but 1-bicyclo[1.1.1]pentyl radical does not, even though the two ring opening reactions are computed to be about equally exothermic (Lee, M.-S.; Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1995, 117, 10353)
201. Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1988, 110, 7229
202. See also: Schäfer, J.; Szeimies, G. Tetrahedron Lett. 1988, 5253
203. Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1988, 110, 4710
204. Renzoni, G. E.; Yin, T.-K.; Borden, W. T. J. Am. Chem. Soc. 1986, 108, 7121
205. Subsequently, the dehalogenation reaction was successfully performed in the gas phase and led to the matrix isolation of 33, n = 1. Radziszewski, J. G.; Yin, T.-K.; Renzoni, G. E.; Hrovat, D. A.; Borden, W. T.; Michl, J. J. Am. Chem. Soc. 1993, 115, 1454
206. Strozier, R. W.; Caramella, P.; Houk, K. N. J. Am. Chem. Soc. 1979, 101, 1340
207. Haddon, R. C. Phil. Trans. R. Soc. London A 1993, 343, 53
208. Smith, J. M.; Hrovat, D. A.; Borden, W. T.; Allan, M.; Asmis, K. R.; Bulliard, C.; Haselbach, E.; Meier, U. C. J. Am. Chem. Soc. 1993, 115, 3816
209. Nicolaides, A.; Smith, J. M.; Kumar, A.; Barnhart, D.; Borden, W. T. Organometallics 1995, 14, 3475
210. Allan, M.; Bulliard, C.; Smith, J. M.; Hrovat, D. A.; Borden, W. T.; Grimme, S. Chem. Phys. 1997, 225, 153
211. Branan, B. M.; Paquette, L. A.; Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1992, 114, 774
212. McKee, M. L. J. Phys. Chem. 1986, 90, 4908
213. Koch, W.; Liu, B.; DeFrees, D. J. J. Am. Chem. Soc. 1988, 110, 7325
214. Saunders, M.; Laidig, K.; Wiberg, K. B.; Schleyer, P.; von, R. J. Am. Chem. Soc. 1988, 110, 7652
215. Della, E. W.; Gill, P. M. W.; Schiesser, C. H. J. Org. Chem. 1988, 53, 4354
216. Mergelsberg, I.; Langhals, H.; Rüchardt, C. Chem. Ber. 1983, 116, 360
217. The coefficients in the LUMO of 39 indicate that the third type of resonance structure makes a much smaller contribution than the second to the bonding in 39. The large amount of positive charge at the γ carbon is most likely due to polarization of the three C-C bonds to this carbon.
218. The mode by which cubylcation (39) is stabilized (119b) is closely related to the mode of through-bond stabilization of the singlet state of 1,4-dehydrocubane (37). (118a, 118b) Deprotonation of 39 at C-4 would yield 37, and the pair of electrons in the broken C-H bond would occupy the HOMO of 37, which is depicted in Figure 12. In 37, the electrons in the cubyl C-C bonds, which stabilize the positive charge at C-1 of 39, are delocalized into the in-phase combination of AOs at both C-1 and C-4 of 37.
219. Zhang, M.-X.; Eaton, P. E.; Gilardi, R. Angew. Chem., Int. Ed. 2000, 39, 401
220. Hrovat, D. A.; Isborn, C. M.; Kahr, B.; Borden, W. T. Org. Lett. 2008, 10, 4763
221. Review: Kottas, G. S.; Clarke, L. I.; Horinek, D.; Michl, J. Chem. Rev. 2005, 105, 1281
222. For example, the preference of 1,2-difluoroethane for a gauche conformation (134) and the increase in C-F BDEs with increasing alkyl group substitution (135) can be rationalized on this basis.
223. See, inter alia: Epiotis, N. D.; Yates, R. L.; Larson, J. R.; Kirmaier, C. R.; Bernardi, F. J. Am. Chem. Soc. 1977, 99, 8379
224. Brunck, T. K.; Weinhold, F. J. Am. Chem. Soc. 1979, 101, 1700
225. Dionne, P.; St-Jacques, M. J. Am. Chem. Soc. 1987, 109, 2616
226. Rablen, P. R.; Hoffmann, R. W.; Hrovat, D. A.; Borden, W. T. J. Chem. Soc., Perkin Trans. 2 1999, 1719
227. Wu, Y. D.; Kirmse, W.; Houk, K. N. J. Am. Chem. Soc. 1990, 112, 4557
228. Getty, S. J.; Borden, W. T. J. Am. Chem. Soc. 1991, 113, 4334
229. My group's research on the effects of fluorine substituents in a variety of reactions has been reviewed in: Borden, W. T. Chem. Commun. 1998, 1919
230. Getty, S. J.; Hrovat, D. A.; Xu, J. D.; Barker, S. A.; Borden, W. T. J. Chem. Soc., Faraday Trans. 1994, 90, 1689
231. Tian, F; Lewis, S. B.; Bartberger, M. D.; Dolbier, W. R., Jr.; Borden, W. T. J. Am. Chem. Soc. 1998, 120, 6187
232. Adam, W.; Borden, W. T.; Burda, C.; Foster, H.; Heidenfelder, T.; Heubes, M.; Hrovat, D. A.; Kita, F.; Lewis, S. B.; Scheutzow, D.; Wirz, J. J. Am. Chem. Soc. 1998, 120, 593
233. Hoffmann, R. J. Am. Chem. Soc. 1968, 90, 11475
234. Reviews: Berson, J. A. In Rearrangements in Ground And Excited States; de Mayo, P., Ed.; Academic Press: New York, 1980; Vol. 1, pp 311-390.
235. Gajewski, J. J. Hydrocarbon Thermal Isomerizations; Academic Press: New York, 1981; pp 27-35.
236. Berson, J. A.; Pedersen, L. D. J. Am. Chem. Soc. 1975, 97, 238
237. Berson, J. A.; Pedersen, L. D.; Carpenter, B. K. J. Am. Chem. Soc. 1976, 98, 122 See also: Cianciosi, S. J.; Ragunathan, N.; Freedman, T. R.; Nafie, L. A.; Baldwin, J. E. J. Am. Chem. Soc. 1990, 112, 8204
238. Cianciosi, S. J.; Ragunathan, N.; Freedman, T. R.; Nafie, L. A.; Lewis, D. K.; Glenar, D. A.; Baldwin, J. E. J. Am. Chem. Soc. 1991, 113, 1864
239. Getty, S. J.; Davidson, E. R.; Borden, W. T. J. Am. Chem. Soc. 1992, 114, 2085
240. Baldwin, J. E.; Yamaguchi, Y.; Schaefer, H. F., III. J. Phys. Chem. 1994, 98, 7513
241. The conversation that led to our collaboration took place at the San Diego Zoo, where Barry and I had spent part of a Saturday between two chemistry conferences. In order to illustrate my hypothesis, that angular momentum would be conserved in ring closure, I was holding my arms, bent at the elbow, in front of me and conrotating them and disrotating them, like the AOs that form the scissile bond in coupled cyclopropane ring opening and ring closure. I was so engrossed in explaining my hypothesis to Barry that it took me a while to realize our fellow zoo-goers were casting quizzical glances at the person who looked like he might be practicing an exotic, oriental, martial art.
242. Hrovat, D. A.; Fang, S.; Borden, W. T.; Carpenter, B. K. J. Am. Chem. Soc. 1997, 119, 5253
243. Doubleday, C., Jr.; Bolton, K.; Hase, W. L. J. Am. Chem. Soc. 1997, 119, 5251
244. Getty, S. J.; Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1994, 116, 1521
245. Dolbier, W. R., Jr.; Enoch, H. O. J. Am. Chem. Soc. 1977, 99, 4532
246. Buchwalter, S. L.; Closs, G. L. J. Am. Chem. Soc. 1975, 97, 3857
247. Buchwalter, S. L.; Closs, G. L. J. Am. Chem. Soc. 1979, 101, 4688
248. Coms, F. D.; Dougherty, D. A. Tetrahedron Lett. 1988, 29, 3753
249. Adam, W.; Grabowski, S.; Platsch, H.; Hannemann, K.; Wirz, J.; Wilson, R. M. J. Am. Chem. Soc. 1989, 111, 751
250. Coms, F. D.; Dougherty, D. A. J. Am. Chem. Soc. 1989, 111, 6894
251. Adam., W.; Platsch, H.; Wirz, J. J. Am. Chem. Soc. 1989, 111, 6896
252. Xu, J. D.; Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1994, 116, 4888
253. Zhang, D. Y.; Hrovat, D. A.; Abe, M.; Borden, W. T. J. Am. Chem. Soc. 2003, 125, 12823
254. Abe, M.; Adam, W.; Borden, W. T.; Hattori, M.; Hrovat, D. A.; Nojima, M.; Nozaki, K.; Wirz, J. J. Am. Chem. Soc. 2004, 126, 574
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