Synthesis of Potential Ambra Odorants: 5,5,9‐trimethyldecalyl derivatives

Ohloff, G.; Näf, Ferdinand; Decorzant, René; Thommen, Walter; Sundt, E.

doi:10.1002/hlca.19730560425

Cited by 59 publications

(23 citation statements)

References 64 publications

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“…The assignments of the 1 H spectrum for synthetic compound 3 are in good agreement with the partial data reported previously for natural and synthetic samples, 4,5,12,17 except for a small shifting in the signals. However, a full assignment, including all coupling constants and multiplicities, was never published before, and is given in Table 1.…”

Section: Resultssupporting

confidence: 85%

LTA‐mediated synthesis and complete assignment of ¹H and ¹³C NMR data of two natural 11‐nordrimanes: isonordrimenone and polygonone

Moreno‐Osorio

Espinoza

Cuéllar

et al. 2007

Magnetic Reson in Chemistry

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Section: Resultssupporting

confidence: 85%

LTA‐mediated synthesis and complete assignment of ¹H and ¹³C NMR data of two natural 11‐nordrimanes: isonordrimenone and polygonone

Moreno‐Osorio

Espinoza

Cuéllar

et al. 2007

Magnetic Reson in Chemistry

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“…The epoxidation of 7b with mCPBA (mchloroperbenzoic acid) gave only 15a a in accordance with the reported selectivity. 29,30) …”

Section: Resultsmentioning

confidence: 99%

Selective Allylic Hydroxylation of Octahydronaphthalene Derivatives with a Bridgehead Double Bond Using Electrochemical Method with Iron Picolinate Complexes

Okamoto

Funaki

Nobuchika

et al. 2005

CHEMICAL & PHARMACEUTICAL BULLETIN

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Oxygenation reactions are very important in steroid metabolism and biosynthesis.1-3) Many investigations on biomimetic oxygenation systems using iron(III) picolinate (Fe III (PA) 3 ) or iron(II) picolinate (Fe II (PA) 2 ) complexes as catalysts have been reported under various conditions and in various solvents, [4][5][6][7][8] but direct 7a-hydroxylation is not easy and most reported allylic hydroxylations involve multistep reactions via other functionalized compounds [9][10][11][12][13][14] or afford low yield or stereoselectivity. [15][16][17] We have been developing a 7a-hydroxylation system for steroids, [18][19][20] and we reported in a preceding paper that the combination of electrolysis and the Fe III (PA) 3 /O 2 /CH 3 CN system gave good results in the hydroxylation of cholesteryl acetate. 21)On the other hand, functionalization, especially oxygenation, of octahydronaphthalenes or decalin derivatives is also very important because many bioactive or natural compounds contain a skeleton resembling the AB fused ring of cholesterol.22-24) Therefore, we wished to identify the required structural factors for regio-and stereoselective direct 7a-hydroxylation of steroids by our electrochemical method, as well as to extend the range of applicability of this method for allylic a-hydroxylation of small cyclic compounds.In this report, we describe the iron picolinate-induced hydroxylation reactions of octahydronaphthalene derivatives 5b, 6b and 7b as simple models for allylic oxygenation of steroids or other decalin derivatives. Results and DiscussionThe substrates 5b-7b were prepared by benzoylation of the corresponding octahydronaphthalenols 5a-7a. [25][26][27] Both 5b and 6b have an alkene moiety at a similar position to C5-C6 of cholesterol. However, the double bond of 7b is not located at the bridgehead of the fused ring. We applied Showa Pharmaceutical University; 3-3165 Higashi-tamagawagakuen, Machida, Tokyo 194-8543, Japan. Received October 23, 2004; accepted November 11, 2004; published online November 22, 2004 The combination of electrolysis and the Fe III (PA) 3 /O 2 /CH 3 CN system was investigated for allylic hydroxylation of octahydronaphthalene derivatives. Substrates with a bridgehead double bond gave the allylic alcohol with a a-preference, while non-bridgehead olefin did not react smoothly. This system is a useful tool for a a-selective allylic hydroxylation of octahydronaphthalene derivatives with a bridgehead double bond as model compounds for the AB fused ring of cholesterols.

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“…-In parallel to the central activity of developing an industrial synthesis of Cetalox (( AE )-1), there was also a research program directed towards the search for new fragrance ingredients even more powerful than ( AE )-1. In this context, it was realized that this new acid-mediated cyclization reaction could also be applied to the preparation of closely related analogues of ( AE )-1 which satisfied the structural requirements of the triaxial rule, a useful empirical theory of the 1970s related to the ambergris-type odor [13]. In this rule, a multi-point interaction between a dimethyl-trans-decalin skeleton and the complementary receptor site is considered to be associated with the axial orientation of the substituents R', R'', and R a , as shown in structure A (Scheme 7).…”

Section: Synthesis Of Ambroxmentioning

confidence: 98%

Cetalox^® and Analogues: Synthesis via Acid‐Mediated Polyene Cyclizations

Snowden

2008

Chemistry & Biodiversity

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Using a novel, acid-mediated cyclization methodology, a direct access to Cetalox ((+/-)-1; a commercially important ambergris-type odorant) and various structurally related didehydro (i.e., 19, 26, and 30) and tetradehydro (i.e., 28 and 37/38) analogues is described. Treatment of either (E,E)-14 or (E)-15 with an excess of FSO(3)H in 2-nitropropane at -90 degrees stereospecifically afforded (+/-)-1 in 40 and 42% yield, respectively. Under similar conditions, cyclization of (E)-18 or 20 furnished 19 in 60 and 64% yield, respectively. Analogously, using an excess of ClSO(3)H in CH(2)Cl(2) at -80 degrees, 26 is formed with high stereoselectivity by cyclization of either (E)-24 or (Z)-25 (52 and 31% yield, resp.); in the same manner, 28 was prepared from 27 (22% yield). The same principle was applied to the synthesis of racemic Superambrox (30), via cyclization of 35, but only with poor selectivity (22%) and low yield (7%). Another approach via cyclization of (E)-40 under solvolysis conditions (excess TFA in CH(2)Cl(2) at -10 degrees) gave a higher yield (15%) with improved selectivity (43%). Finally, cyclization of 34 (1:1 diastereoisomer mixture) afforded 37/38 (10:1) in 27% yield. The qualitative organoleptic properties of 19, 26, 28, 30, and 37/38 (10:1) are briefly discussed.

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Synthesis of Potential Ambra Odorants: 5,5,9‐trimethyldecalyl derivatives

Cited by 59 publications

References 64 publications

LTA‐mediated synthesis and complete assignment of ¹H and ¹³C NMR data of two natural 11‐nordrimanes: isonordrimenone and polygonone

LTA‐mediated synthesis and complete assignment of ¹H and ¹³C NMR data of two natural 11‐nordrimanes: isonordrimenone and polygonone

Selective Allylic Hydroxylation of Octahydronaphthalene Derivatives with a Bridgehead Double Bond Using Electrochemical Method with Iron Picolinate Complexes

Cetalox^® and Analogues: Synthesis via Acid‐Mediated Polyene Cyclizations

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Synthesis of Potential Ambra Odorants: 5,5,9‐trimethyldecalyl derivatives

Cited by 59 publications

References 64 publications

LTA‐mediated synthesis and complete assignment of 1H and 13C NMR data of two natural 11‐nordrimanes: isonordrimenone and polygonone

LTA‐mediated synthesis and complete assignment of 1H and 13C NMR data of two natural 11‐nordrimanes: isonordrimenone and polygonone

Selective Allylic Hydroxylation of Octahydronaphthalene Derivatives with a Bridgehead Double Bond Using Electrochemical Method with Iron Picolinate Complexes

Cetalox® and Analogues: Synthesis via Acid‐Mediated Polyene Cyclizations

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LTA‐mediated synthesis and complete assignment of ¹H and ¹³C NMR data of two natural 11‐nordrimanes: isonordrimenone and polygonone

LTA‐mediated synthesis and complete assignment of ¹H and ¹³C NMR data of two natural 11‐nordrimanes: isonordrimenone and polygonone

Cetalox^® and Analogues: Synthesis via Acid‐Mediated Polyene Cyclizations