Proximity Effects. XLII. The Reaction of Lithium Diethylamide with cis- and trans-4-Octene Oxide<sup>1</sup>

Cope, Arthur C.; Heeren, James K.

doi:10.1021/ja01092a021

Cited by 45 publications

(20 citation statements)

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(1 reference statement)

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“…A by-product in conversion of the ethyl epoxide to the ethyl allylic alcohol (12A) is the corresponding chlorohydrin (13A, 18%) formed by the Markovnikov addition of HC1 to the allylic alcohol. Reaction of the ethyl epoxide (2A) with lithium diethylamide (Cope and Heeren, 1965;Crandall and Chang, 1967) is not an appropriate route to the allylic alcohol (12A) because there is extensive ether cleavage.…”

Section: Synthesesmentioning

confidence: 99%

Synthesis and morphogenetic activity of derivatives and analogs of aryl geranyl ether juvenoids

Hammock¹,

Gill²,

Casida³

1974

J. Agric. Food Chem.

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Section: Synthesesmentioning

confidence: 99%

Synthesis and morphogenetic activity of derivatives and analogs of aryl geranyl ether juvenoids

Hammock¹,

Gill²,

Casida³

1974

J. Agric. Food Chem.

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“…(4,5). In the steroid field, a variant of this reaction has been widely used in the preparation of y-hydroxy-a,P-unsaturated ketones by base catalysed rearrangement of p , y epoxy ketones such as 3 b and 6 b (eq.…”

mentioning

confidence: 99%

Reactions of steroidal 4,5- and 5,6-epoxides with strong bases

Holland¹

1983

Can. J. Chem.

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, 2165 (1983). A series of C-3 oxygcnated and unsubstituted (4,5)a, (4,5)P, (5,6)cu, and (5.6)P cpoxy stcroids has been prcparcd, and the reactions of these compounds with strong bases (potassium rert-butoxide, LDA, and LDEA) wcrc investigatcd. Only LDEA gavc rise to product formation; P climination of the cpoxidc to give a P-hydroxy olefin was obscrvecl in this case. The regioselcctivity of product formation is consistcnt with a mechanism of rcarrangcmcnt involving removal of a hydrogen locatcd syr~ to the epoxide oxygen. In some cascs, a dirccting influence from a polar substitucnt (OH) of the starting matcrial was also apparent. The '" nmr spectra of the steroidal cpoxidcs used in this study were assigned; these data are diagnostic of the confornlation of ring A of (4,5)cu and (4,5)P epoxy steroids.HERBERT L. HOLLAND et JAHANGIR. Can. J. Chcm. 61, 2165Chcm. 61, (1983 On a prCparC une serie d'Cpoxy stCroides du typc (4,5)cu, (4.5)P. (5,6)cu et (5,6)P oxygCnCs en position C-3 ct non substituks et on a CtudiC lcurs rkactions avec des bases fortes (rert-butylate de potassium, LDA et LDEA). Seulc la LDEA conduit h la formation de produits; on a observC dans ce cas une elimination P de I'Cpoxydc qui conduit la P-hydroxy olCfine. La rCgiosClectivitC de la formation du produit cst cn accord avec un mCcanismc de transposition qui impliquc une Climination d'hydrogtne situC en position syn de I'oxygtne de 1'Cpoxydc. On note Cgalcmcnt dans quelqucs cas, unc influcncc directrice du substituant polaire (OH) du produit de dCpart. On a identifit Ics spcctrcs de rmn du I3C des Cpoxy stCroidcs utilisdcs; ces donnkcs permettcnt de prCdirc la conformation du cycles A dcs ( 4 . 5 )~~ et (4.5)P Cpoxy stdro~des.[Traduit par Ic journal]The base catalysed rearrangement of epoxides to allylic alcohols, involving P-hydrogen abstraction (eq.

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“…We postulate that the sixmembered transition state accessible to the 35 a·DATMP coordination complex leading to allylic alcohol 40 is not available to the 35 b·DATMP complex (Scheme 6). [44,45] As such, the latter undergoes Lewis acid-induced epoxide ring-opening to generate the tertiary carbocation leading to 41 via the diethylaluminum enol ether intermediate. To help substantiate this theory, isolated epoxide 35 a was subjected to the same reaction conditions.…”

Section: Wwwchemeurjorgmentioning

confidence: 99%

Assessing Synthetic Strategies: Total Syntheses of (±)‐Neodolabellane‐Type Diterpenoids

Valente

Organ

2008

Chemistry A European J

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Two strategies, namely a cross-metathesis/ring-closing metathesis and Pd-catalyzed Stille allylation/Nozaki-Hiyama-Kishi coupling, are examined for the preparation of neodolabellane-type diterpenoids 1 and 2. Whereas the first approach possessed synthetic limitations, the latter was successfully employed to provide compounds 1 and 2 in 8.8% (14 steps) and 8% (15 steps) overall yields, respectively.

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Proximity Effects. XLII. The Reaction of Lithium Diethylamide with cis- and trans-4-Octene Oxide¹

Cited by 45 publications

References 1 publication

Synthesis and morphogenetic activity of derivatives and analogs of aryl geranyl ether juvenoids

Synthesis and morphogenetic activity of derivatives and analogs of aryl geranyl ether juvenoids

Reactions of steroidal 4,5- and 5,6-epoxides with strong bases

Assessing Synthetic Strategies: Total Syntheses of (±)‐Neodolabellane‐Type Diterpenoids

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Proximity Effects. XLII. The Reaction of Lithium Diethylamide with cis- and trans-4-Octene Oxide1

Cited by 45 publications

References 1 publication

Synthesis and morphogenetic activity of derivatives and analogs of aryl geranyl ether juvenoids

Synthesis and morphogenetic activity of derivatives and analogs of aryl geranyl ether juvenoids

Reactions of steroidal 4,5- and 5,6-epoxides with strong bases

Assessing Synthetic Strategies: Total Syntheses of (±)‐Neodolabellane‐Type Diterpenoids

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Proximity Effects. XLII. The Reaction of Lithium Diethylamide with cis- and trans-4-Octene Oxide¹