Stereoselectivity of the retro-ene reaction of 2-vinylcyclohexanols

Marvell, Elliot N.; Rusay, Ronald J.

doi:10.1021/jo00441a003

Cited by 20 publications

(4 citation statements)

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“…Hydrogenation of 3 by PtO 2 catalyst gave the saturated ketone 4 in an overall isolated yield of 73%. Thus, the present reaction may offer a novel method for the catalytic ring-opening reaction of general 2-vinylcycloalkanols …”

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confidence: 97%

Ruthenium-Catalyzed β-Allyl Elimination Leading to Selective Cleavage of a Carbon−Carbon Bond in Homoallyl Alcohols

et al. 1998

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confidence: 97%

Ruthenium-Catalyzed β-Allyl Elimination Leading to Selective Cleavage of a Carbon−Carbon Bond in Homoallyl Alcohols

et al. 1998

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“…Consider, for example, the product ratio for eqn. ( 13) chemistry (14). The literature report equates the ratio of rate constants kjke to the product ratio (14) while application of eqn.…”

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confidence: 99%

“…( 13) chemistry (14). The literature report equates the ratio of rate constants kjke to the product ratio (14) while application of eqn. (6) indicates the correct relationship to be as shown in eqn.…”

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confidence: 99%

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The Curtin-Hammett principle and the Winstein-Holness equation: new definition and recent extensions to classical concepts

Seeman¹

1986

J. Chem. Educ.

195

131

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One measure of value of a scientific principle is its frequency and scope of usage. Concepts are frequently developed for specific applications. It will be argued for the cases discussed herein, and perhaps more generally, that the original applications of a particular theory can serve unwittingly as an unfortunate limitation: the full development of the theory may be impeded if the theory is "locked into" its original application by a unidirectional mindset of potential users.The simplest kinetic system which exemplifies the effect of conformation on chemical reactivity is shown in eqn. (1). Here, two different conformations A2 and A3 of the same molecule react with rate constants k2i and k34, respectively, to give two different products, Ai and A4. One can easily envision extensions of eqn. (1) to more complex situations involving conformations, some (or all) of which react to form one or more products. A significant variable is the magnitude of the rate constants for conformational interconversion kc (k23 and k32 in eqn. (1) relative to the rate constants for reactivity kr (k2\ and k34). Because the rates of conformational interconversion are generally, though not invariably, larger than their rates of chemical reactivity, (I), we shall limit ourselves in this and the next four sections below to the Curtin-Hammett/Winstein-Holness conditions, namely kc » kr (hi3, k32 » k2i, k34 in eqn. (1).

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Reductions by Metal Alkoxyaluminum Hydrides

Málek

1985

Organic Reactions

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Since the discovery of the reducing properties of diborane (1939), alkali metal borohydrides (1943), and alkali metal aluminohydrides (1946) by H. I. Schlesinger, H. C. Brown, W. G. Brown, and co‐workers, considerable effort has been expended to enhance the versatility and selectivity of these widely used hydride reagents. Whereas diborane exhibits medium reaction large differences exist between sodium borohydride and lithium aluminum hydride. In contrast to the reducing action of sodium borohydride, limited originally to aldehydes, ketones, and acid chlorides, lithium aluminum hydride readily attacks almost all reducible groups. The first progress in bridging this gap in reactivity can be traced to the availability of reagents that are easily prepared by addition of Lewis acids such as boron and aluminum halides to sodium borohydride and lithium aluminum hydride; in this manner diborane, chloroaluminum hydrides, and aluminum hydride have been made accessible as reducing agents. Parallel development led to sodium alkoxyborohydrides with generally higher reactivity than the parent hydride and to alkoxyaluminum hydrides, with markedly lower reactivity and increased chemoselectivity. On the other hand, the reducing capability of sodium borohydride and lithium aluminum hydride has been enhanced by the use of metal salt–hydride systems. A large number of other complex metal hydrides have gained importance as selective reducing agents: lithium aluminum hydride–nitrogen base complexes, sodium cyanoborohydride, lithium cyanoborohydride, sulfurated sodium borohydride, zinc borohydride, diisobutylaluminum hydride, alkylaluminum compounds such as triisobutylaluminum, and tri‐ n ‐butyltin hydride. Sterically hindered organoboranes such as lithium tri‐ sec ‐butylborohydride (L‐Selectride) exhibit excellent selectivity in reduction reactions. High asymmetric induction can be achieved with some chiral organoboranes. Lithium triethylborohydride (Super‐Hydride) is a selective and exceptionally powerful reducing agent. These complex metal hydrides often provide better regio‐ and stereoselectivities than those achieved with alkoxy‐substituted hydrides; nevertheless, the alkoxyhydrides are readily available and continue to be widely used as reducing agents. The purpose of this chapter is to present a critical review of reductions of the following compounds by metal alkoxyaluminum hydrides, alkoxyaluminum hydrides, and chiral metal alkoxyaluminohydride complexes: hydrocarbons, peroxides, ozonides, halogen compounds, unsaturated alcohols, aromatic alcohols, ethers, 1,2‐oxides, aldehydes, ketones, quinones, acetals, and ketals. The literature is covered through December 1981. Important papers that appeared through September 1982 are also reviewed. Some reactions relating to other than reducing properties of these hydrides are included for completeness. The emphasis is on the scope, limitations, and synthetic utility of the hydrides in reduction reactions and on the optimum conditions for their application as reducing agents. Currently accepted views of reaction mechanisms are discussed. Comparisons with reductions by other complex metal hydrides are limited to the most important transformations of the functional groups.

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Stereoselectivity of the retro-ene reaction of 2-vinylcyclohexanols

Cited by 20 publications

References 3 publications

Ruthenium-Catalyzed β-Allyl Elimination Leading to Selective Cleavage of a Carbon−Carbon Bond in Homoallyl Alcohols

Ruthenium-Catalyzed β-Allyl Elimination Leading to Selective Cleavage of a Carbon−Carbon Bond in Homoallyl Alcohols

The Curtin-Hammett principle and the Winstein-Holness equation: new definition and recent extensions to classical concepts

Reductions by Metal Alkoxyaluminum Hydrides

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