Steroids. CXLIII.<sup>1</sup> Transannular Reactions at Saturated Carbon Atoms. Part 1. C-3,9-Oxide Formation

Bowers, Alan R.; Denot, E.

doi:10.1021/ja01503a051

Cited by 31 publications

(14 citation statements)

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“…(27)); 2.03 (s, AcO ); 2.41 (t, J 11.6, HÀC(17)); 2.65 (d, J 13.7, HÀC(8)); 4.72 (m, HÀC(3)); 4.85, 5.00 (2 s, CH 2 (18)). 13 C-NMR (50 MHz, CDCl 3 ): 219.4 (s, C(14)); 170.6 (s, MeCOO ); 147.9 (s, C(13)); 114.9 (t, C(18)); 73.2 (d, C(3)); 56.3 (d, C(8)); 54.0 (d, C(17)); 44.5 (d, C(9)); 44.0 (d, C(5)); 39.4 (t, C(24)); 37.1 (d, C(20)); 36.3 (t, C(1)); 36.3 (s, C(10)); 34.2 (t, C(4)); 33.8 (t, C(22)); 33.6 (t, C(7)); 29.3 (t, C(6)); 27.9 (d, C(25)); 27.5 (t, C(2)); 26.7 (t, C(16)); 26.4 (t, C(12)); 25.4 (t, C(15)); 24.5 (t, C(23)); 22.7 (q, C(27)); 22.5 (q, C(26)); 21.4 (q, MeCOO ); 17.6 (q, C(21)); 11.9 (q, C(19)). MS (27)); 2.04 (s, AcOÀC(3)); 2.07 (s, AcOÀC(15)); 2.63 (m, HÀC(8)); 4.72 (m, HÀC(3)); 4.91, 5.10 (2 s, CH 2 (18)); 5.41 (dd, J 2.8, 4.1, HÀC(15)).…”

Section: Scheme 10mentioning

confidence: 99%

“…Rotation of the side chain in E: rotation angle vs. the distance O(14)´´´C (22) and vs. the energy HÀC(8)); 4.69 (m, HÀC(3)); 5.09, 5.20 (2 s, CH 2 (18)); 5.26 (t, J 7, HÀC(12)); 5.38 (d, J 5.1, HÀC(15)). 13…”

Section: Scheme 10mentioning

confidence: 99%

“…The structures 6 ± 9 were deduced from their analytical and spectroscopic data (IR, 1 H-NMR, 13 C-NMR, MS). In addition, structure 6 was unequivocally confirmed by Xray analysis 2 ).…”

mentioning

confidence: 99%

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13,14-Seco-steroids: A New Type of Modified Steroids Containing a Nine-Membered Ring

Bjelaković¹,

Lorenć

Pavlović

et al. 1999

HCA

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Oxidations of 14α‐hydroxy‐5α‐cholestan‐3β‐yl acetate (5) with lead tetraacetate under thermal or photolytic conditions or in the presence of iodine proceed mainly by fragmentation of the C(13)−C(14) bond to give as the primary products the 13,18‐didehydro‐13,14‐seco derivative 6 and the (E )‐Δ12‐13,14‐seco ketone 11, respectively. Further transformations of these compounds under conditions of their formation afforded, in addition, the acetoxy derivatives 7 – 9 (from 6), and the D‐homo‐C‐nor compound 12 and (12R,13R)‐epoxide 13 (from 11). Unexpectedly, the photolytic lead‐tetraacetate oxidation of 5 resulted partly (to ca. 20%) in a reversible fragmentation involving scission and recombination of the C(8)−C(14) bond followed by formation of the 14β,22‐ether 10. Possible mechanisms for the observed transformations are discussed.

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Section: Scheme 10mentioning

confidence: 99%

Section: Scheme 10mentioning

confidence: 99%

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13,14-Seco-steroids: A New Type of Modified Steroids Containing a Nine-Membered Ring

Bjelaković¹,

Lorenć

Pavlović

et al. 1999

HCA

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“…Reaction of 2,3,4,4,5-Pentachloro-2-cyclopentenone (IX) with Methanol. 3,3a,4,5,6,.-A 25.4-g. sample of 2,3,4,4,5-pentachloro-2cyclopentenone (IX) was refluxed with 100 ml. of methanol.…”

Section: Xxivamentioning

confidence: 99%

The Reactions of Alcohols with Highly Chlorinated Cyclopentenones

Weil¹,

Linder²

1963

J. Org. Chem.

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Alcoholysis of tetrachlorocyclopentene-3,5-dione and hexachloro-2-cyclopentenone yielded l-hydroxy -2,4,4trichlorocyclopentene-3,5-dione and 3-hydroxy-2,4,4,5,5-pentachloro-2-cyclopentenone, respectively. In the presence of base, the same ketones underwent ring opening with alcohol to yield esters. 2,3,4,4,5-Pentachloro-2-cyclopentenone was found to react with methanol to yield a product hitherto known as the methanol adduct of hexachloroindone and which now has been shown to be 4-carbomethoxy-2,

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“…Reduction of the 1 1-0xo-18,20P-Zactone (13) with Sodium Borohydride.22-A solution of sodium borohydride (19.3 mg, 0.5 mmol) in absolute ethanol (2.5 ml) and 1~ aqueous sodium hydroxide (0.2 ml, 0.2 mmol) was added to a stirred solution of the ll-oxo-18,20~-lactone (13) (44.1 mg, 0.1 mmol) in tetrahydrofuran (2.5 nil) and the mixture was stirred a t 41,- 45 "C for 2 days. The mixture was then poured on to ice-water (10 ml) and 2111 aqueous hydrochloric acid was added to neutrality.…”

Section: P 18-epoxy-3a-(tetrahydropyran-2-yzoxy)-5~-pregnane-mentioning

confidence: 99%

18-Substituted steroids. Part 6. Synthesis of 3α,18-dihydroxy-11β,18-epoxy-5β-pregnan-20-one (21-deoxy-3α,5β-tetrahydroaldosterone)

Crump¹,

Kirk²,

Miller³

1980

J. Chem. Soc., Perkin Trans. 1

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Deoxy-3a,5P-tetahydroaldosterone (5) has been prepared from 3a-acetoxy-20~-hydroxy-5~-pregnan-l1 -one (7) via the hypoiodite reaction sequence (lead tetra-acetate-iodine-hv; oxidation) followed by reduction and rearrangement of 18,20~-lactone-l1 -ketone (1 3) to the 18,ll ~-lactone-20P-alcohoI ( 14). Reduction of the 18,ll P-lactone-20P-alcohol (1 4) with di-isobutylaluminium hydride afforded the 18,ll p-hemiacetal-2OPalcohol (1 71, which gave the 18,2O-diacetate (1 8). Treatment of the diacetate with acidic methanol gave the 18-methoxy-20(3-acetate (1 9) by selective solvolysis at C-18. Removal of the 20-acetate with lithium aluminium hydride, followed by oxidation with Collins' reagent, and acid hydrolysis of the protecting groups then afforded 21 -deoxy-3a,5P-tetrahydroaldosterone (5) in 20% overall yield.

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Steroids. CXLIII.¹ Transannular Reactions at Saturated Carbon Atoms. Part 1. C-3,9-Oxide Formation

Cited by 31 publications

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13,14-Seco-steroids: A New Type of Modified Steroids Containing a Nine-Membered Ring

13,14-Seco-steroids: A New Type of Modified Steroids Containing a Nine-Membered Ring

The Reactions of Alcohols with Highly Chlorinated Cyclopentenones

18-Substituted steroids. Part 6. Synthesis of 3α,18-dihydroxy-11β,18-epoxy-5β-pregnan-20-one (21-deoxy-3α,5β-tetrahydroaldosterone)

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Steroids. CXLIII.1 Transannular Reactions at Saturated Carbon Atoms. Part 1. C-3,9-Oxide Formation

Cited by 31 publications

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13,14-Seco-steroids: A New Type of Modified Steroids Containing a Nine-Membered Ring

13,14-Seco-steroids: A New Type of Modified Steroids Containing a Nine-Membered Ring

The Reactions of Alcohols with Highly Chlorinated Cyclopentenones

18-Substituted steroids. Part 6. Synthesis of 3α,18-dihydroxy-11β,18-epoxy-5β-pregnan-20-one (21-deoxy-3α,5β-tetrahydroaldosterone)

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Steroids. CXLIII.¹ Transannular Reactions at Saturated Carbon Atoms. Part 1. C-3,9-Oxide Formation