Stéréochimie de l'addition d'organostanniques allyliques aux aldéhydes

Servens, C.; Pereyre, Michel

doi:10.1016/s0022-328x(00)86867-9

Cited by 78 publications

(12 citation statements)

References 2 publications

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“…For example, the anti and syn products 6 (X = H) and 9 are obtained from the (E)-and (Z)-but-2-enylstannanes 4 (X = H) and 7, consistent with participation of the transition structures 5 and 8. 5 1-Substituted (E)-but-2-enylstannanes 4 (X = Me, OR) react with aldehydes on heating (Scheme 2) with excellent stereoselectivity in favour of the anti-(Z)-but-3-en-1-ols 6 (X = Me, OR). 6,7 The formation of Z double bonds in these reactions is consistent with participation of the transition structures 5 (X = Me, OR) in which the substituent next to tin is axial.…”

Section: Introductionmentioning

confidence: 99%

Control and applications of remote asymmetric induction using allylmetal reagents

Thomas¹

1997

Chem. Commun.

100

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Treatment of hydroxy-and alkoxy-substituted allylstannanes with tin(IV) halides effects transmetallation and the stereoselective formation of allyltin trihalides. These react with aldehydes and imines derived from glyoxylates with useful levels of remote asymmetric induction. Aspects of this chemistry are discussed, together with the conversion of the products into tetrahydrofurans and dihydropyrans.During a study of the chemistry of (S)-4-benzyloxypent-2-enylstannane 1, 1 it was found that stereo-and regio-selective reactions in favour of the 1-substituted syn-(Z)-5-benzyloxyhex-3-en-1-ols 2 were achieved if the allylstannane was treated with tin(iv) chloride for a few minutes at 278 °C followed by addition of an aldehyde (Scheme 1). 2 This reaction attracted our interest because of its high level of 1,5-asymmetric induction. This review discusses the scope of remote asymmetric induction using allyltin reagents.

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Section: Introductionmentioning

confidence: 99%

Control and applications of remote asymmetric induction using allylmetal reagents

Thomas¹

1997

Chem. Commun.

100

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“…For many years, it has been known that ( E )‐but‐2‐enylstannanes 1 react with aldehydes on heating to give the anti ‐homoallylic alcohols 2 , which is consistent with participation of the chair‐like, six‐membered cyclic transition structure 3 4. During early work on the development of an asymmetric version of this reaction, [1‐alkoxy‐( E )‐but‐2‐enyl]stannanes 4 were found to react with aldehydes on heating with very high stereocontrol in favor of the ( Z )‐1,2‐ anti ‐products 5 , although high temperatures, ≥100°C, were required for nonactivated aldehydes 5.…”

Section: Remote Stereocontrol Using Allylstannanesmentioning

confidence: 84%

Remote stereocontrol using functionalized allylmetal reagents

Thomas

2007

The Chemical Record

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Alk-2-enyl(trialkyl)stannanes with heteroatom substituents at the 4-, 5-, and 6-positions are transmetallated stereoselectively using tin(IV) halides to generate allyltin trihalides, which react with aldehydes to give (3Z)-homoallylic alcohols with efficient 1,5-, 1,6-, and 1,7-stereocontrol. This chemistry has been used to develop new strategies for natural product synthesis. Because of the toxicity of organotin reagents and the problems in removing organotin residues from reaction products, alternative procedures that avoid the use of organotin reagents have been investigated. To date, alk-2-enylgermanium reagents have been shown to deliver effective 1,5- and 1,6-stereocontrol, which is analogous to that observed for the organotin compounds. Organobismuth intermediates, which can be generated from allyl bromides and zinc-bismuth(III)iodide, react with aldehydes with efficient 1,5-stereocontrol which is complementary to that observed with the organo-stannanes or -germanes in that (3E)-homoallylic alcohols are obtained.

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“…The uncatalyzed version proceeds through a six-membered cyclic transition state, [52] while with Lewis acid catalysis an open-chain transition state has been proposed. [39,53] Allyltributyltins can be conveniently transmetallated to form more reactive species.…”

Section: Synthesis Of Homoallylic Alcohols General Remarksmentioning

confidence: 99%

“…From the (E)-stannane (E)-21 the threoproduct 22 is formed predominantly (or exclusively) when the reaction is performed at high temperature [52] or under high pressure. [55] Alternatively, the (Z)-21 isomer affords the erythro product 23.…”

Section: Synthesis Of Homoallylic Alcohols General Remarksmentioning

confidence: 99%

Sugar Allyltin Compounds: Preparation and Application in Organic Synthesis

Jarosz

Gaweł

2005

Eur J Org Chem

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General methodology for the preparation of allyltin derivatives is reported, with special attention paid to sugar allyltins. Typical procedures affording such organometallics involve the conversion of partially protected hexoses or pentoses (Sug–CH2OH) into homologated allylic alcohols (Sug–CH=CH–CH2OH), which are further transformed into the primary or secondary sugar allyltin derivatives of the general formula Sug–CH=CH–CH2SnR3, (E)/(Z) ratio ≈ 5:1, or Sug–CH*(SnR3)–CH=CH2 (single isomer with the (S)‐configuration at the newly created chiral center*). Controlled Lewis acid‐induced fragmentation of these hexose‐derived organometallics provides highly oxygenated dienoaldehydes with the (E) geometry across the internal double bond: CH2=CH–CH=CH–[CH(OR)]3–CHO. The (Z)‐dienoaldehydes are also available by thermal fragmentation of the secondary sugar allyltins. Both these synthons ((E) and (Z)) can be further converted into highly functionalized derivatives of bicyclo[4.3.0]nonene and bicyclo[4.4.0]decene. Stereochemical aspects of reactions between sugar allyltins and sugar aldehydes (in the presence of Lewis acids or under high pressure) are also discussed. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

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Stéréochimie de l'addition d'organostanniques allyliques aux aldéhydes

Cited by 78 publications

References 2 publications

Control and applications of remote asymmetric induction using allylmetal reagents

Control and applications of remote asymmetric induction using allylmetal reagents

Remote stereocontrol using functionalized allylmetal reagents

Sugar Allyltin Compounds: Preparation and Application in Organic Synthesis

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