The Novel Adamantane Isomer 2,5‐Trimethylenenorbornane (Tricycio‐[5.3.0.<sup>3,9</sup>]decane, 4‐Homotwistbrendane)

Känel, Hans‐Ruedi; Capraro, Hans‐Georg; Ganter, C.

doi:10.1002/hlca.19820650335

Cited by 4 publications

(2 citation statements)

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“…Solvolysis of the p-toluenesulfonate 2 of protoadamant-4-en-loendo-01 yielded among others the allylic alcohols 3 and 4 with the desired C-skeleton [2]. Subsequent conversions of the iatters led to 1.…”

Section: Discussionmentioning

confidence: 98%

“…Its treatment with 10% Pd/C [9] under H2-atmosphere and subsequent reduction with LiA1H4 gave a mixture of diastereomeric alcohols 13 (87%), which was converted to a mixture of methanesulfonates 14 (88%). Subsequent elimination with sodium anthracene [lo] led to the olefine 15 (51%), which very recently we already had prepared by an independent route [2] and had converted by hydrogenation to the title compound 2,5-trimethylenenorbornane (1) [2].…”

Section: J)mentioning

confidence: 99%

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A Further Synthetic Approach to the Adamantane Isomer 2, 5‐Trimethylenenorbornane (Tricyclo [5.3.0.0^3,9]decane, 4‐Homotwistbrendane)

Känel¹,

Ganter²

1982

Helvetica Chimica Acta

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SummaryA further synthetic approach to 2,5-trimethylenenorbornane (1; tricyclo- [5.3.0.03,9]decane, 4-homotwistbrendane), a member of the 'adamantaneland', is described starting from methyl 5-0x0-2endo-norbornanecarboxylate (5). The required C2-chain was introduced by a Wittig-Horner reaction and the ring closure of the trimethylene bridge achieved by an acyloin condensation.In the course of our studies on isomeric tricyclic hydrocarbons of the 'adamantaneland' '), we recently described a first synthesis of the title isomer, 2,5-trimethylenenorbornane (1)'). Solvolysis of the p-toluenesulfonate 2 of protoadamant-4-en-loendo-01 yielded among others the allylic alcohols 3 and 4 with the desired C-skeleton [2]. Subsequent conversions of the iatters led to 1.In view of further investigations on the adamantane rearrangement of 1, especially with specifically labelled analogues, we report a second synthetic approach to 1 and derivatives thereof, starting from the properly 2,5-difunctionalized norbornane 5. As the only evaluated synthesis of 5 (31 is an unspecific one, we decided to prepare 5 from the known ester 6 [4] by the following route: epoxidation and lactonization of 6 with trifluoroperacetic acid [S] gave the known [6] hydroxy lactone 7 (94%), which was oxidized to the keto lactone 8 (80%) with

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Section: Discussionmentioning

confidence: 98%

Section: J)mentioning

confidence: 99%

A Further Synthetic Approach to the Adamantane Isomer 2, 5‐Trimethylenenorbornane (Tricyclo [5.3.0.0^3,9]decane, 4‐Homotwistbrendane)

Känel¹,

Ganter²

1982

Helvetica Chimica Acta

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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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ChemInform Abstract: THE NOVEL ADAMANTANE ISOMER 2,5‐TRIMETHYLENENORBORNANE (TRICYCLO(5.3.0.03,9)DECANE, 4‐HOMOTWISTBRENDANE)

Kaenel¹,

Capraro²,

Ganter³

1982

Chemischer Informationsdienst

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The Novel Adamantane Isomer 2,5‐Trimethylenenorbornane (Tricycio‐[5.3.0.^3,9]decane, 4‐Homotwistbrendane)

Abstract: A synthesis of the novel C10H16 hydrocarbon 2,5‐trimethylenenorbornane (tricyclo[5.3.0.03,9]decane, 1), one of the 19 members of the ‘adamantaneland’, and its Lewis‐acid‐catalyzed rearrangement is described.

Cited by 4 publications

References 10 publications

A Further Synthetic Approach to the Adamantane Isomer 2, 5‐Trimethylenenorbornane (Tricyclo [5.3.0.0^3,9]decane, 4‐Homotwistbrendane)

A Further Synthetic Approach to the Adamantane Isomer 2, 5‐Trimethylenenorbornane (Tricyclo [5.3.0.0^3,9]decane, 4‐Homotwistbrendane)

Reductions by Metal Alkoxyaluminum Hydrides

ChemInform Abstract: THE NOVEL ADAMANTANE ISOMER 2,5‐TRIMETHYLENENORBORNANE (TRICYCLO(5.3.0.03,9)DECANE, 4‐HOMOTWISTBRENDANE)

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The Novel Adamantane Isomer 2,5‐Trimethylenenorbornane (Tricycio‐[5.3.0.3,9]decane, 4‐Homotwistbrendane)

Abstract: A synthesis of the novel C10H16 hydrocarbon 2,5‐trimethylenenorbornane (tricyclo[5.3.0.03,9]decane, 1), one of the 19 members of the ‘adamantaneland’, and its Lewis‐acid‐catalyzed rearrangement is described.

Cited by 4 publications

References 10 publications

A Further Synthetic Approach to the Adamantane Isomer 2, 5‐Trimethylenenorbornane (Tricyclo [5.3.0.03,9]decane, 4‐Homotwistbrendane)

A Further Synthetic Approach to the Adamantane Isomer 2, 5‐Trimethylenenorbornane (Tricyclo [5.3.0.03,9]decane, 4‐Homotwistbrendane)

Reductions by Metal Alkoxyaluminum Hydrides

ChemInform Abstract: THE NOVEL ADAMANTANE ISOMER 2,5‐TRIMETHYLENENORBORNANE (TRICYCLO(5.3.0.03,9)DECANE, 4‐HOMOTWISTBRENDANE)

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The Novel Adamantane Isomer 2,5‐Trimethylenenorbornane (Tricycio‐[5.3.0.^3,9]decane, 4‐Homotwistbrendane)

A Further Synthetic Approach to the Adamantane Isomer 2, 5‐Trimethylenenorbornane (Tricyclo [5.3.0.0^3,9]decane, 4‐Homotwistbrendane)

A Further Synthetic Approach to the Adamantane Isomer 2, 5‐Trimethylenenorbornane (Tricyclo [5.3.0.0^3,9]decane, 4‐Homotwistbrendane)