The Conservation of Orbital Symmetry
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Woodward R. B., 1967, Aromaticity. Special Publication No. 21, 217
Coulson C. A., 1961, Valence
Coulson C. A., 1964, The Chemistry of Alkenes
Heilbronner E., 1968, Das HMO‐Modell und seine Anwendung
Throughout this paper molecular orbitals are symbolized in terms of the atomic orbitals whose interaction gives the actual molecular orbital; since we are in general interested only in nodal properties we ignore the fact that the coefficients – and thus the relative sizes – of the resultant atomic orbital contributions are not all identical.
Salem L., 1966, The Molecular Orbital Theory of Conjugated Systems
Streitwieser A., 1961, Molecular Orbital Theory for Organic Chemists
Herzberg G., 1950, The Electronic Structure of Diatomic Molecules
We could of course label the levels with their proper symmetry designations appropriate to the D2hsymmetry of the approach. We deliberately use the symmetric (S) and antisymmetric (A) labels since the nodal properties of the orbitals are then most clearly discernible.
The rule follows directly from perturbation theory and the correlation of higher energy with increasing number of nodes in a wave function.
A similar situation arises in other areas of chemistry. The n→π*transition in formaldehyde is electric‐dipole forbidden. The source of the small intensity observed is still disputed. In the cases of acetaldehyde or of unsymmetrically substituted ketones the symmetry element which made the formaldehyde transition electric‐dipole forbidden is removed. The transition becomes allowed. Does it therefore jump to a high intensity? Not at all; the intensity remains practically unchanged. This is because theessentialsymmetry that of the local environment of the carbonyl group is unchanged.
Fukui K., 1965, Modern Quantum Chemistry, 49
Winter R. E. K., Tetrahedron Letters, 1965, 1207
R.CriegeeandG.Bolz unpublished work;
D.Seebach personal communication. The value forn= 1 is estimated fromJ. I. Brauman L. E. Ellis and AE. E. van Tamelen J. Amer. chem. Soc.88 846 (1966). A more detailed study of the case
(58) n= 4 has been reported recently:J. J. Bloomfield J. S. McConaghy jr. andA. G. Hortmann Tetrahedron Letters 1969 3723.
Huisgen R., Tetrahedron Letters, 1964, 3381
Quinkert G., Tetrahedron Letters, 1965, 3009
Theuer W. J., Chem. Commun., 1965, 468
Inhoffen H. H., 1959, Fortschr. Chem. org. Naturstoffe, 17, 70
Lythgoe B., Proc. chem. Soc., 1959, 141
Courtot P., Tetrahedron Letters, 1968, 1091
Muszkat K. A., J. chem. Soc., 662
Vogel E., Tetrahedron Letters, 1965, 391
Marvell E. N., Tetrahedron Letters, 1965, 385
Glass D. S., Tetrahedron Letters, 1965, 377
Ziegler K., 1955, Angew. Chem., 67, 301
Baird M. S., Tetrahedron Letters, 1967, 1379
Ghosez L., Tetrahedron Letters, 1967, 2773
Jefford C. W., Tetrahedron Letters, 1966, 6317
Whitham G. H., Chem. Commun., 1967, 294
Nazarov I. N., 1957, Zh. Obsh. Khim., 27, 693
R.Lehr D.Kurland andR. B.Woodward unpublished observations.Cf. Dorothy Kurland Dissertation Harvard (1967);
RolandLehr Dissertation Harvard (1968).
Johnstone R. A. W., J. chem. Soc. C, 1968, 1805
Bishop M. J., J. chem. Soc. C, 1969, 1712
Bates R. B., Tetrahedron Letters, 1969, 977
G. J.Fonken personal communication;
Radlick P., Tetrahedron Letters, 1967, 4901
Cookson R. C., Chem. Ind., 1961, 21
Masamune S., Chem. Commun., 1969, 542
Vogel E., 1964, Angew. Chem., 76, 432
1964, Angew. Chem. internat. Edit., 3, 442
The terms suprafacial and antarafacial were first used in our discussion of sigmatropic reactions;cf.ref. [3].
We [Accounts of Chem. Res.1 17 (1968)] and others have earlier usedcisandtransto designate the geometrical relationships here denominatedsupraandantara. However the use ofcisandtransas nomenclatural qualifiers is firmly established and their employment in different senses – often of necessity simultaneously – can be cumbersome and confusing especially in discussing multicomponent combinations.
Warrener R. N., 1966, Rev. pure appl. Chem., 16, 117
Robson R., J. chem. Soc., 1964, 2153
Frey H. M., 1966, Advances in Physical Organic Chemistry, 170
Kraft K., Tetrahedron Letters,, 1967, 4357
Wiberg K. B., Tetrahedron Letters,, 1968, 1235
Turner R. B., Tetrahedron Letters, 1965, 997
Huisgen R., 1964, The Chemistry of Alkenes, 739
Wassermann A., 1965, The Diels‐Alder Reaction
1964, Angew. Chem. internat. Edit., 3, 653
Prinzbach H., Tetrahedron Letters, 1965, 2959
Crowley K. J., Tetrahedron Letters, 1965, 2863
W. G.Dauben personal communication;
Dauben W. G., Tetrahedron Letters, 1961, 565
Saunderson C. P., Tetrahedron Letters, 1961, 573
Childs R. F., J. chem. Soc. C, 1967, 201
1968, Angew. Chem. internat. Edit., 7, 537
Here and in the sequel we use the device of placing a negative sign before the bracket whenever a reaction is characterized in terms of its products.
H. R.Nace personal communication.
de Mayo P., Proc. chem. Soc., 1964, 84
Kraft K., Tetrahedron Letters, 1967, 4357
K.Houk Dissertation Harvard (1968).
Cookson R. C., Chem. Commun., 1966, 15
Itǒ S., 1966, Bull. chem. Soc. Japan, 39, 135
Itǒ S., Tetrahedron Letters, 1967, 1059
W.vonE.Doering personal communication.
Cookson R. C., J. chem. Soc. C, 1967, 473
J. chem. Soc. C, 1965, 2009
Hoffmann H. M. R., J. chem. Soc. B, 1968, 57
Walls F., Tetrahedron Letters, 1965, 1577
Huisgen R., 1964, The Chemistry of Alkenes, 739
Kropp P. J., 1967, Organic Photochemistry, 1, 1
Barton D. H. R., J. chem. Soc., 1961, 1215
Barton D. H. R., J. chem. Soc., 1958, 140
Chapman O. L., Tetrahedron Letters, 1963, 2049
H. E.Zimmerman 17th National Organic Symposium of the American Chemical Society Bloomington Indiana 1960 Abstracts p. 31;
Barton D. H. R., J. chem. Soc., 1958, 140
Cocker W., J. chem. Soc., 1957, 3416
Barton D. H. R., J. chem. Soc., 1960, 4596
Only the consequences of an addition on the double bond next to R are sketched. Of course the addition on the opposite side is feasible and will double the number of possible products.
D. I.Schuster personal communication.
Williams J. R., Chem. Commun., 1967, 194
Zimmerman H. E., 1968, J. Amer. chem. Soc., 90, 4192
Brewer J. P. N., Chem. Commun., 1967, 811
Cookson R. C., Tetrahedron Letters, 1962, 615
Staab H. A., Tetrahedron Letters,, 1966, 743
1968, Angew. Chem. internat. Edit., 7, 646
Prinzbach H., Tetrahedron Letters, 1967, 3713
1966, Angew. Chem. internat. Edit., 5, 1039
Prinzbach H., 1967, Chimia, 21, 469
Takahashi M., Tetrahedron Letters, 1968, 3387
Longuet‐Higgins H. C., 1959, Theoretical Organic Chemistry. The Kekulé Symposium, 17
W.von E. Doering personal communication;
Flowers M. C., J. chem. Soc., 1961, 3547
Ellis R. J., J. chem. Soc., 1964, 959
Elliot C. J., J. chem. Soc., 1965, 345
J. chem. Soc. A, 1966, 553
Frey H. M., J. chem. Soc., 1962, 3981
Branton G. R., J. chem. Soc., 1966, 1342
Rabinowitch B. S., 1960, J. Amer. chem. Soc., 86, 5996
W. R.Roth personal communication.
Hurst J. J., J. chem. Soc., 1960, 2864
Cookson R. C., Tetrahedron Letters, 1965, 3955
Cookson R. C., 1960, Chemistry in Britain, 5, 6
Baggiolini E., 1969, Chimia, 23, 181
Glass D. S., Tetrahedron Letters, 1966, 999
Grigg R., Chem. Commun., 1967, 1192
W. R.RothandJ.König personal communication.
McLean S., Tetrahedron Letters, 1964, 2385
Roth W. R., Tetrahedron Letters, 1964, 1009
Weth E., Proc. chem. Soc., 1964, 59
Weidler A., 1964, Acta chem. scand., 18, 1484
Crowley K. J., Proc. chem. Soc., 1964, 17
Prinzbach H., Tetrahedron Letters, 1964, 2959
Rhoads S. J., 1963, Molecular Rearrangements, 655
Miyashi T., Tetrahedron Letters, 1967, 3433
Akhtar M., Tetrahedron Letters, 1965, 509
1963, Angew. Chem. internat. Edit., 2, 688
Hug R., 1969, Chimia, 23, 108
Pocker Y., 1963, Molecular Rearrangements
Koptyug V. A., Izv. Akad. Nauk SSSR, 1965, 201
Makisumi Y., Tetrahedron Letters, 1967, 6393
Zimmerman H. E., 1963, Molecular Rearrangements, 372
Baldwin J. E., Chem. Commun., 1968, 537
Blackburn G. M., Chem. Commun., 1968, 186
Bates R. B., Tetrahedron Letters, 1968, 417
Trost B. M., Tetrahedron Letters, 1968, 3327
Baldwin J. E., Tetrahedron Letters, 1968, 5029
Stevens T. S., J. chem. Soc., 1930, 2107
Johnstone R. A. W., J. chem. Soc., 1955, 4487
Millard B. J., J. chem. Soc., 1963, 3397
Cram D. J., 1965, Fundamentals of Carbanion Chemistry, 223
J. E.Baldwin personal communication.
Glass D. S., Proc. chem. Soc., 1963, 276
Ellis R. J., Proc. chem. Soc., 1964, 221
J. chem. Soc., 1964, 5578
Crandall J. K., Tetrahedron Letters, 1967, 1717
Ohloff G., Tetrahedron Letters, 1965, 3795
Roth W. R., 1966, Chimia, 20, 229
McGreer D. E., Proc. chem. Soc., 1964, 415
Conia J. M., Tetrahedron Letters, 1966, 129
Rouessac F., Tetrahedron Letters, 1965, 3313
P.Dowd personal communication;
I.Fleming personal communication.
Baldwin J. E., Tetrahedron Letters, 1966, 2953
Ellis R. J., J. chem. Soc. A, 1966, 553
W. D.Walters personal communication.
Frey H. M., J. chem. Soc. A, 1967, 509
Fukui K., 1964, Molecular Orbitals in Chemistry, Physics, and Biology, 525
Alder K., 1953, Fortschr. Chem. org. Naturstoffe, 10, 1
Wassermann A., J. chem. Soc., 1935, 825
J. chem. Soc., 1936, 432
Cookson R. C., Chem. Commun., 1966, 15
K.Houk Dissertation Harvard (1968).
Cookson R. C., J. chem. Soc., 1964, 5416
Hill R. K., Chem. Commun., 1967, 619
Brown J. M., Proc. chem. Soc., 1965, 226
Staab H. A., Tetrahedron Letters, 1965, 54
Hoffmann H. M. R., J. chem. Soc. B, 1968, 1182
Yankelevich S., Tetrahedron Letters, 1967, 4945
Carpino L. A., Chem. Commun., 1966, 494
However the corresponding aryl‐substituted case proceeds in a non‐stereospecific manner (personal communication fromL. A. Carpino).
Neureiter N. P., 1963, J. Amer. chem. Soc., 85, 1210
Lemal D. M., 1966, J. Amer. chem. Soc., 88, 528
Staudinger H., 1912, Die Ketene
Huisgen R., Tetrahedron Letters, 1968, 4485
Binsch G., Tetrahedron Letters, 1968, 4497
1964, Angew. Chem. internat. Edit., 3, 753
1968, Angew. Chem. internat. Edit., 7, 221
Huisgen R., Tetrahedron Letters, 1968, 4491
Smirnov‐Zamkov I. V., 1952, Doklady Akad. Nauk SSSR, 83, 869
Smirnov‐Zamkov I. V., 1953, Ukr. Khim. Zhur., 21, 233
Roberts J. D., 1962, Organic Reactions, 12, 1
1968, Angew. Chem. internat. Edit., 7, 646
1966, Angew. Chem. internat. Edit., 5, 669
Fukui K., Tetrahedron Letters, 1965, 2009
Fukui K., Tetrahedron Letters, 1966, 251
Aromaticity. Special Publication of The Chemical Society No. 21 London 1967 p. 177.
van der Lugt W. Th. A. M., Chem. Commun., 1968, 1235
Laidler K. J., 1955, The Chemical Kinetics of Excited States
1949, Rev. mod. Physics, 41, 527
Oosterhoff L. J., 1961, Tetrahedron, 16, 151
Syrkin Ya. K., Izv. Akad. Nauk SSSR, 1959, 238
Balaban A. T., 1966, Rev. Roum. Chimie, 11, 1097
1967, Rev. Roum. Chimie, 12, 875
Mathieu J., Bull. Soc. chim. France, 1957, 1509
Miller S. I., 1968, Advances in Physical Organic Chemistry, 185
Millie P., Bull. Soc. chim. France, 1966, 4031
Orchin M., 1967, The Importance of Antibonding Orbitals
Kosower E. M., 1968, An Introduction to Physical Organic Chemistry
Červinka O., 1967, Chem. Listy, 61, 1036
1968, Chem. Listy, 62, 321
Houbiers J. P. M., 1966, Chem. Weekblad, 62, 61
Dewar M. J. S., 1969, The Molecular Orbital Theory of Organic Chemistry
Fukui K., 1964, Molecular Orbitals in Chemistry, Physics and Biology, 513
Fukui K., 1965, Modern Quantum Chemistry, 49
McCapra F., Chem. Commun., 1968, 155