Regioselective cyclopropanation reactions using iodonium ylides: Synthesis of prostaglandin precursors

Moriarty, Robert M.; May, Eric J.; Guo, Linghong; Prakash, Om

doi:10.1016/s0040-4039(97)10620-7

Cited by 34 publications

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“…Methyl ester 13a was subjected to diazo transfer [20] to yield the diazoacetoacetate 14a. Reaction of 13a,b,d with PhI(OAc) 2 and KOH in MeOH, as described by Moriarty et al [16], gave the phenyliodonium ylides 15a,b,d. This latter transformation was much less problematic than that of the malonate-derived ylide 7b.…”

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“…In view of the instability of ylide 7b, we turned our attention to the prostaglandin precursor 16, which has been synthesized in the past by intramolecular cyclopropanation of the diazoacetoacetates 14a [14] and 14c [15] and from the phenyliodonium ylide 15a [16] (Scheme 3). The keto esters 13a,b,d were synthesized from (2E,4E)-deca-2,4-dienal (9) according to established procedures with some minor modifications.…”

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Carbenoid Pathways in Copper-Catalyzed Intramolecular Cyclopropanations of Phenyliodonium Ylides

Müller¹,

Boléa²

2001

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The enantioselectivity of the copper-catalyzed intramolecular cyclopropanation of allyl diazomalonates and the corresponding phenyliodonium ylides was investigated with a series of chiral, non-racemic ligands. The reaction of 6b in the presence of the bis [dihydrooxazole] ligand Xa in refluxing 1,2-dichloroethane proceeded to 8b with an enantiomer excess (ee) of up to 72% under optimized conditions. In contrast, 8b resulting from reaction of ylide 7b with the same ligand, but in CH 2 Cl 2 at 08, had an ee of only 30%. With other ligands, diazomalonate 6b reacted with a lower enantioselectivity than ylide 7b, however. The intramolecular cyclopropanation of the acetoacetate-derived phenyliodonium ylide 15b afforded 16b with 68% ee with ligand Xa, but the corresponding diazo compound was unreactive when exposed to chiral copper catalysts. The observation of asymmetric induction in the Cu-catalyzed reactions of the ylides 7 and 15 is consistent with a carbenoid mechanism; however, the discrepancy of the enantioselectivities observed between diazomalonate 6b and ylide 7b suggests a competing unselective pathway for cyclopropanation outside of the coordination sphere of copper.[4] decomposition of phenyliodonium ylides [5] affords products typical for carbene or metal carbenoid intermediates. The mechanism of these reactions is, however, controversial. Carbene or carbenoid pathways have often been proposed or assumed, but experimental evidence in support of these hypotheses is scarce. Some years ago, we have investigated the decomposition of some diazo compounds and the corresponding phenyliodonium ylides in the presence of [Rh II (carboxylato)] catalysts. Both precursors afforded the same selectivities in the intermolecular cyclopropanation of substituted styrenes and in the intramolecular competition for cyclopropanation vs. CH insertion. In addition, identical enantioselectivities resulted when the intramolecular CH insertion of a diazoacetoacetate and the corresponding phenyliodonium ylide was carried out in the presence of Ikegamis chiral [Rh II (carboxylato)] catalyst [6]. These results are consistent with a carbenoid mechanism.However, the majority of the synthetically useful reactions with phenyliodonium ylides have been carried out under Cu-catalysis, and for Cu-catalysts the mechanism is not established. Moriarty et al. investigated the intramolecular cyclopropanation of ylide 1 to the tricyclic ketone 4 in the presence of [CuCl] (Scheme 1) [7]: the reaction proceeded in yields of 76 to 90%; surprisingly, it also occurred in the absence of catalyst, albeit in lower yield. The authors proposed a mechanism in which the electrophilic iodonium center attacks the CC bond to afford a carbenium ion 2, which, subsequently, undergoes transannular alkylation to yield 3. Reductive elimination of PhI from 3 finally produces the cyclopropane 4. The catalytic effect of Cu I , in turn, was ascribed to electron transfer. A carbene mechanism was specifically ruled out.

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Carbenoid Pathways in Copper-Catalyzed Intramolecular Cyclopropanations of Phenyliodonium Ylides

Müller¹,

Boléa²

2001

HCA

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“…Ôá υëßäéá του éωäßου åßíáé ÷ñÞóéìá óτηí οñãáíéêÞ óύíθåóη ëüãω τηò éêáíüτητÜò τουò íá óυììåτÝ÷ουí óå åíäοìοñéáêÝò áíτéäñÜóåéò êυêëοπñοπáíοποßηóηò, 4,[15][16][17][18][19][20] êáθþò êáé óå 1,3-äéποëéêÝò êυêëοπñοóθÞêåò. 21,22 ÊáτÜ τηí θåñìéêÞ ìå Rh II -êáτáëυüìåíη áποóύíθåóÞ τουò ëåéτουñãούí ωò êáτÜëëηëá πñüäñοìá äñáóτéêþí åíäéÜìåóωí êáñâåíßωí (Þ êáñâåíοåéäþí).…”

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“…Πéθáíüτáτá, οé ÌÄÄ êáé οé 1,1-ÄÄÄ áíτéäñούí τá÷ύτåñá áπü τοí 1,2-ÄÄÄ ëüãω Ýëëåéøηò óτåñåο÷ηìéêÞò Ç Ýíäåéîη üτé τá éωäο υëßäéá áíτéäñούí πáñουóßá êáτáëυτéêÞò ποóüτητáò óυìπëüêωí του Rh(II) ìÝóω ó÷ηìáτéóìού τωí áíτßóτοé÷ωí êáñâåíßωí (Þ êáñâåíοåéäþí) êáθéåñþθηêå ãéá τηí πåñßπτωóη του PhI=C(CO 2 Me) 2 32 êáé Üëëωí áíÜëοãωí éωäο υëéäßωí.Ôá πñοúüíτá 53 που πñοêύπτουí áπü τηí Rh II êáτáëυüìåíη áíτßäñáóη åßτå τωí éωäο υëéäßωí, åßτå τωí áíÜëοãωí äéáaeωåíþóåωí ìå óτυñÝíéο, áëëυëο âåíaeüëéο êáé öáéíυëο áêåτυëÝíéο, åßíáé áêñéâþò τá ßäéá (Ó÷Þìá 36) 88,89,[93][94][95]. Ïé áíτéäñÜóåéò τωí äéáaeωåíþóåωí ìå áυτÜ τá υποóτñþìáτá Ý÷åé áποäåé÷θåß üτé ëáìâÜíουí ÷þñá ìÝóω êáñâåíßωí.Ç áíτßäñáóη êυêëοπñοπáíοποßηóηò äåí πåñéοñßaeåτáé ìüíο óå äéáìοñéáêÝò áíτéäñÜóåéò, áëëÜ âñßóêåé åöáñìοãÞ ìå éäéáßτåñο åíäéáöÝñοí êáé óå åíäοìοñéáêÝò áíτéäñÜóåéò 4,17,96. Ç êáτáëυτéêÞ áποóύíθåóη τωí éωäο υëéäßωí åßíáé åîáéñåτéêÜ ÷ñÞóéìη áíτßäñáóη ωò ìÝθοäοò êυêëοποßηóηò, ìÝóω åíäοìοñéáêÞò êυêëοπñοóθÞêηò Þ πáñåìâοëÞò.…”

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“…Πéο óυãêåêñéìÝíá, η åíäοìοñéáêÞ êυêëοπñοπáíοποßηóη του éωäο υëéäßου 54 CuCl Ç êáτáëυüìåíη ìå ÷áëêü áποóύíθåóη του éωäο υëéäßου 56 οäηãåß óτηí áíáìåíüìåíη υποêáτåóτηìÝíη τåτñáëüíη 57 (Ó÷Þìá 38) 96. Ïìοßωò, το éωäο υëßäéο 58 υößóτáτáé regio êáé óτåñåοåêëåêτéêÞ åíäοìοñéáêÞ êυêëοπñοπáíοποßηóη, êáé ó÷ηìáτßaeåé τηí Ýíωóη 59, η οποßá áποτåëåß åíäéÜìåóο êëåéäß ãéá τη óύíθåóη τωí πñοóτáãëáíäéíþí (Ó÷Þìá 39) 17. Ç ìåτáëëο-êáτáëυüìåíη áποóύíθåóη τωí éωäο υëéäßωí âñßóêåé åöáñìοãÞ óτηí áóύììåτñη óύíθåóη 19,71,74,97.…”

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Αντιδράσεις Των Ιωδο Υλιδίων Β-Δισουλφονών Και Β-Δικετονών

Νυχάς¹

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ÐÅÑÉÅ×ÏÌÅÍÁ ÅÉÓÁÃÙÃÇ 1. Õëßäéá του Ιωäßου 1.1 ΙóτοñéêÞ áíáäñοìÞ 1.2 ÃåíéêÞ äοìÞ τωí υëéäßωí του éωäßου 1.3 ΠáñáóêåυÞ τωí éωäο υëéäßωí êáé áποóύíθåóη 1.4 ÁíτéäñÜóåéò τωí éωäο υëéäßωí 1.4.1 ÁíτéäñÜóåéò ìå ηëåêτñοíéüöéëá áíτéäñáóτÞñéá 1.4.2 ÁíτéäñÜóåéò ÊυêëοπñοóθÞêηò 1.4.3 ÁíτéäñÜóåéò Ôñáíóυëéäßωóηò 1.4.4 Áaeéñéäéíßωóη êáé áìßíωóη 1.5 Ιωäο υëßäéá öáéíοëþí Þ 1,4-äßποëá 1.6 Ιωäο υëßäéá τωí â-äéóουëöοíþí ÁÐÏÔÅËÅÓÌÁÔÁ-ÓÕAEÇÔÇÓÇ 2. Ιωäο υëßäéá â-äéóουëöοíþí 2.1 ΠáñáóêåυÞ éωäο υëéäßωí â-äéóουëöοíþí êáé áποóύíθåóη 2.2 ÁíτéäñÜóåéò éωäο υëéäßωí â-äéóουëöοíþí ìå íοñâοíυëÝíéο êáé éωäοáëêÜíéá 2.3 ×áëêüíåò. Óύíθåóη êáé åöáñìοãÝò 2.4 ÁíτéäñÜóåéò éωäο υëéäßωí â-äéóουëöοíþí ìå ÷áëêüíåò 3. Ιωäο υëßäéá â-äéêáñâοíυëéêþí åíþóåωí 3.1 Óύíθåóη τωí â-äéêáñâοíυëéêþí éωäο υëéäßωí êáé áποóύíθåóη 3.2 ÁíτéäñÜóåéò êυêëοπñοóθÞêηò éωäο υëéäßωí 3.2.1 ÁíτéäñÜóåéò ìå áëêÝíéá 3.2.2 ÁíτéäñÜóåéò ìå áëêßíéá 3.2.3 ÁíτéäñÜóåéò ìå äéÝíéá 3.2.4 ÁíτéäñÜóåéò ìå öουñÜíéá 3.2.5 ÁíτéäñÜóåéò ìå θåéοêáñâοíυëéêÝò åíþóåéò 3.2.6 ÁíτéäñÜóåéò ìå äéöáéíυëο êåτÝíη ÐÅÉÑÁÌÁÔÉÊÏ ÌÅÑÏÓ 4.1 ÓυóêåυÝò-¼ñãáíá 4.2 Óύíθåóη τωí â-äéóουëöοíþí êáé τωí áíτßóτοé÷ωí éωäο υëéäßωí 4.3 ÁíτéäñÜóåéò éωäο υëéäßωí â-äéóουëöοíþí ìå íοñâοíυëÝíéο ii 4.4 ÁíτéäñÜóåéò éωäο υëéäßωí τωí â-äéóουëöοíþí µå áëêυëοúωäßäéá 4.5 Óύíθåóη ×áëêοíþí 4.6 ÁíτéäñÜóåéò éωäο υëéäßωí â-äéóουëöοíþí ìå ÷áëêüíåò 4.7 Óύíθåóη τωí â-äéêáñâοíυëéêþí éωäο υëéäßωí êáé áποóύíθåóη 4.8 ÁíτéäñÜóåéò ìå áëêÝíéá 4.9 ÁíτéäñÜóåéò ìå áëêßíéá 4.10 ÁíτéäñÜóåéò ìå äéÝíéá 4.11 ÁíτéäñÜóåéò ìå öουñÜíéá 4.12 ÁíτéäñÜóåéò ìå θåéοêáñâοíυëéêÝò åíþóåéò 4.13 ÁíτéäñÜóåéò ìå äéöáéíυëο êåτÝíη ÐÅÑÉËÇΨÇ 5. Πåñßëηøη ÂÉÂËÉÏÃÑÁÖÉÁ 6. Âéâëéοãñáößá 141 iii Ðñüëïãïò Ôá υëßäéá του éωäßου áποτåëούí ìéá τÜîη åíþóåωí του υπåñóθåíούò éωäßου, οé οποßåò âñßóêουí ποéêßëåò åöáñìοãÝò óτηí οñãáíéêÞ óύíθåóη. Óêοπüò τηò πáñούóáò åñãáóßáò Þτáí η ìåëÝτη τωí áíτéäñÜóåωí τωí éωäο υëéäßωí τωí â-äéóουëöοíþí, êáθþò êáé τωí êυêëéêþí â-äéêáñâοíυëéêþí éωäο υëéäßωí. ÁíáëυτéêÜ åîåτÜóτηêáí οé áíτéäñÜóåéò τωí éωäο υëéäßωí â-äéóουëöοíþí ìå íοñâοíυëÝíéο, πáñουóßá Þ ìη, áëêυëο éωäéäßωí, êáθþò êáé οé áíτéäñÜóåéò τουò ìå ìéá ποéêéëßá ÷áëêοíþí. ÅîåτÜóτηêáí, åπßóηò, οé áíτéäñÜóåéò τωí éωäο υëéäßωí τηò 1,3êυêëοåîáíοäéüíηò êáé 1,3-êυêëοπåíτáíοäéüíηò ìå πëηθþñá äéποëáñüöéëωí óå äéÜöοñåò óυíθÞêåò áíτßäñáóηò, οé οποßåò Ýäωóáí τá πñοéüíτá êυêëοπñοóθÞêηò ìå ìÝτñéåò åþò êáëÝò áποäüóåéò. Ïé áíτéäñÜóåéò τωí éωäο υëéäßωí τωí â-äéóουëöοíþí ìå áëêυëο éωäßäéá οäÞãηóáí óτá áíτßóτοé÷á áëêυëáëοãοíßäéá êáé óå áëêυëο υποêáτåóτηìÝíåò äéóουëöüíåò. Ïé áíτéäñÜóåéò τωí éωäο υëéäßωí τωí â-äéóουëöοíþí ìå íοñâοíυëÝíéο οäÞãηóáí óτá éíäáíéêÜ πáñÜãωãá, åíþ η áíτßäñáóη ìå íοñâοíυëÝíéο πáñουóßá éωäοìåθáíßου οäÞãηóå óτο πñοúüí ηëåêτñοíéüöéëηò πñοóθÞêηò óτοí äéπëο äåóìü του íοñâοíυëåíßου. Ïé áíτéäñÜóåéò τωí äéò(áñυëοóουëöοíυëο)éωäο υëéäßωí ìå ÷áëêüíåò οäÞãηóáí óå éíäáíéêÜ πáñÜãωãá, óå πñοéüíτá äéÜóπáóηò, πáñåìâοëÞò óτοí οëåöéíéêü C-H äåóìü êáé óå öëáâáíüíåò. Ïé áíτéäñÜóåéò τωí â-äéêáñâοíυëéêþí éωäο υëéäßωí ìå áëêÝíéá, áëêßíéá, äéÝíéá, öουñÜíéá, θåéού÷á äéποëáñüöéëá êáé êåτÝíåò, οäÞãηóáí óτá áíτßóτοé÷á πñοúüíτá êυêëοπñοóθÞêηò, που...

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Intermolecular Metal‐Catalyzed Carbenoid Cyclopropanations

2001

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The metal‐catalyzed decomposition of diazo compounds in the presence of alkenes is a well‐established reaction. Since the original Organic Reactions review on the reaction of ethyl diazoacetate with alkenes and aromatic compounds in 1970, several new developments have revolutionized this area of chemistry. Most notably, major advances have been made in catalyst design such that highly chemoselective, diastereoselective and enantioselective carbenoid transformations can now be achieved. Furthermore, it has been recognized that a wide array of carbenoid structures can be utilized in this chemistry, leading to a broad range of synthetic applications. This chapter comprises coverage of the metal‐catalyzed intermolecular cyclopropanations of diazo compounds containing at least one adjacent electron‐withdrawing group. The coverage of diazoacetate chemistry will be limited to material since 1970 because the previous Organic Reactions review covers the earlier literature. The alkene component is limited to alkenes, dienes, furans, and pyrroles because these are the systems that have resulted in the greatest developments since the 1970 review. Metal‐carbenoid intermediates derived from diazo compounds undergo a variety of useful reactions, including cyclopropanation, insertion, and ylide formation. In recent years several excellent reviews have appeared on various aspects of this chemistry. Three recent reviews have focused on asymmetric intermolecular cyclopropanations. Several books and reviews on carbenoid chemistry have major sections on intermolecular cyclopropanations. Because of the historical central prominence of carbenoids derived from diazoacetates, most reviews have tended to focus on this class of carbenoids. In this chapter, a comparison is presented of the chemical differences that exist among the major classes of carbenoids that contain adjacent electron‐withdrawing groups. The extensive nature of the topic precludes coverage of related reactions such as the metal‐catalyzed decomposition of diazoalkanes, phenyldiazoalkanes, or vinyldiazoalkanes that lack adjacent electron‐withdrawing functionality. Other cyclopropanation reactions such as the Simmons‐Smith reaction, photochemical or thermal decomposition of diazo compounds in the presence of alkenes, and cyclopropanation using stoichiometric metal carbenes are not covered.

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Regioselective cyclopropanation reactions using iodonium ylides: Synthesis of prostaglandin precursors

Cited by 34 publications

References 16 publications

Carbenoid Pathways in Copper-Catalyzed Intramolecular Cyclopropanations of Phenyliodonium Ylides

Carbenoid Pathways in Copper-Catalyzed Intramolecular Cyclopropanations of Phenyliodonium Ylides

Αντιδράσεις Των Ιωδο Υλιδίων Β-Δισουλφονών Και Β-Δικετονών

Intermolecular Metal‐Catalyzed Carbenoid Cyclopropanations

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