Stereochemical and spectroscopic studies on the reaction of allylstannanes with aldehydes

Denmark, Scott E.; Weber, Eric J.; Wilson, Thomas M.; Willson, Timothy M.

doi:10.1016/0040-4020(89)80016-x

Cited by 109 publications

(23 citation statements)

References 39 publications

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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. [54] Figure 8.…”

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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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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“…They proceed via acyclic transition states, the precise conformation of which (that is, antiperiplanar or synclinal) is still under debate. [18] However, the stereochemical outcome is syn. When an equimolar mixture of the enantiomerically pure all-carbonsubstituted stannane (R)-9 and an aldehyde was treated with BF 3 ·OEt 2 , syn-configured, [17] highly enantiomerically enriched homoallylic alcohols were formed in good yields; the diastereoselectivity was reasonably high in all cases ( Table 2, entries 1-5).…”

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confidence: 99%

Enantiospecific Synthesis and Allylation of All‐Carbon‐Substituted α‐Chiral Allylic Stannanes

Schmidtmann

Oestreich

2009

Angew Chem Int Ed

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“…Lewis-Säure-vermittelte Carbonylallylierungen, beispielsweise mit BF 3 ·OEt 2 als Lewis-Säure, [1,2,10] sind erheblich weiter verbreitet als thermische S E 2'-Reaktionen. Sie verlaufen über acyclische Übergangszustände, deren genaue Konformation, also antiperiplanar oder synclinal, noch immer diskutiert wird; [18] unabhängig davon wird jeweils das syn-Produkt erhalten. Beim Versetzen einer äquimolaren Mischung aus unserem enantiomerenreinen nur-Kohlenstoffsubstituierten Stannan (R)-9 und einem Aldehyd mit BF 3 ·OEt 2 entstanden die syn-konfigurierten, [16] hochgradig enantiomerenangereicherten Homoallylalkohole in guten chemischen Ausbeuten; die Diastereoselektivitäten waren in allen Fällen annehmbar (Tabelle 2, Nr.…”

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