A Grignard-Type Addition of Allyl Unit to Aldehydes by Using Bismuth and Bismuth Salt

Wada, Makoto; Ohki, Hidenori; Akiba, Kin‐ya

doi:10.1246/bcsj.63.1738

Cited by 97 publications

(29 citation statements)

References 24 publications

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“…We began with BiCl 3 -mediated allylation39 of ethyl glyoxalate to furnish homoallylic alcohol 92 as an inconsequential mixture (ca. 1:1) of isomers (Scheme 33).…”

Section: Resultsmentioning

confidence: 99%

Spongipyran synthetic studies. Evolution of a scalable total synthesis of (+)-spongistatin 1

Smith¹,

Sfouggatakis²,

Risatti³

et al. 2009

Tetrahedron

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Three syntheses of the architecturally complex, cytotoxic marine macrolide (+)-spongistatin 1 (1) are reported. Highlights of the first-generation synthesis include: use of a dithiane multicomponent linchpin coupling tactic for construction of the AB and CD spiroketals, and their union via a highly selective Evans boron-mediated aldol reaction en route to an ABCD aldehyde; introduction of the C(44)–C(51) side chain via a Lewis acid-mediated ring opening of a glucal epoxide with an allylstannane to assemble the EF subunit; and final fragment union via Wittig coupling of the ABCD and EF subunits to form the C(28)–C(29) olefin, followed by regioselective Yamaguchi macrolactonization and global deprotection. The second- and third- generation syntheses, designed with the goal of accessing one gram of (+)-spongistatin 1 (1), maintain both the first-generation strategy for the ABCD aldehyde and final fragment union, while incorporating two more efficient approaches for construction of the EF Wittig salt. The latter combine the original chelation-controlled dithiane union of the E- and F-ring progenitors with application of a highly efficient cyanohydrin alkylation to append the F-ring side chain, in conjunction with two independent tactics to access the F-ring pyran. The first F-ring synthesis showcases a Petasis-Ferrier union/rearrangement protocol to access tetrahydropyrans, permitting the preparation of 750 mgs of the EF Wittig salt, which in turn was converted to 80 mg of (+)-spongistatin 1, while the second F-ring strategy, incorporates an organocatalytic aldol reaction as the key construct, permitting completion of 1.009 g of totally synthetic (+)-spongistatin 1 (1). A brief analysis of the three syntheses alongside our earlier synthesis of (+)-spongistatin 2 is also presented.

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“…We began with BiCl 3 -mediated allylation39 of ethyl glyoxalate to furnish homoallylic alcohol 92 as an inconsequential mixture (ca. 1:1) of isomers (Scheme 33).…”

Section: Resultsmentioning

confidence: 99%

Spongipyran synthetic studies. Evolution of a scalable total synthesis of (+)-spongistatin 1

Smith¹,

Sfouggatakis²,

Risatti³

et al. 2009

Tetrahedron

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“…As an alternative, Xu et al found nano-Bi to be more effective than regular Bi-powder, although this method had an intrinsic difficulty of preparing Bi-nanoparticles via reduction of Bi(III) salts [35]. These apart, combinations of Bi(III) salts with reducing metals, e.g., Mg-BiCl 3 [36], Fe-BiCl 3 or Zn-BiCl 3 [30], and Al-BiCl 3 [37] have been used. Aqueous NH 4 Cl was also employed as an additive in the Al/BiCl 3 mediated allylation of carbonyls in aqueous THF [38].…”

Section: Introductionmentioning

confidence: 99%

Bi-mediated allylation of aldehydes in [bmim][Br]: a mechanistic investigation

Koli

Chatterjee

Chattopadhyay

et al. 2018

Beilstein J. Org. Chem.

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The inexpensive room temperature ionic liquid (RTIL), [bmim][Br] has been found to be a superior medium for the Bi-mediated Barbier-type allylation of aldehydes compared to other conventional solvents. It plays the dual role of a solvent and a metal activator enabling higher yields of the products in a shorter reaction time using stoichiometric/near-stoichiometric amounts of reagents. Plausibly, [bmim][Br] activates Bi metal by a charge transfer mechanism. The 1H VT-NMR studies suggested that both the allylating species, allylbismuth dibromide and diallylbismuth bromide, are generated in situ.

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“…Recently, there has been a considerable interest in developing organometallic reactions in water, of which allylation of aldehydes and ketones to give homoallylic alcohols has been regarded widely. 1 This reaction has been achieved by using metals such as Mn/Cu, 2 Sn, 3 Zn, 4 Bi, 5 In, 6 Mg, 7 Ga, 8 or organometallic compounds such as diallylmercury, allylmercurybromide, 9 allyltributylstannanes 10 and tetraallylgermane. 11 Previously indium was reported to mediate Barbier-Grignard and pinacol coupling type reactions in water, 6 subsequently, gallium also was used to carry out the Barbier-Grignard and pinacol coupling type reactions in water.…”

Section: Introductionmentioning

confidence: 99%

Nano‐Aluminum Powder Mediated Allylation of Carbonyl Compounds in Aqueous Media

Yuan

Liu

2008

Chin. J. Chem.

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A new and effective Barbier-Grignard allylation of aldehydes or ketones has been carried out with nano-aluminum powder in aqueous 0.1 mol•L -1 NH 4 Cl (aq.) under an atmosphere of nitrogen. Aromatic carbonyl compounds gave homoallylic alcohols in good yields. The effectiveness of reaction was strongly influenced by the steric environment surrounding the carbonyl group. Aliphatic carbonyl compounds proceeded in low yields. The dominant stereoisomer was an erythro-isomer when an ortho-hydroxyl carbonyl compound was reacted under such a reaction condition.

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A Grignard-Type Addition of Allyl Unit to Aldehydes by Using Bismuth and Bismuth Salt

Cited by 97 publications

References 24 publications

Spongipyran synthetic studies. Evolution of a scalable total synthesis of (+)-spongistatin 1

Spongipyran synthetic studies. Evolution of a scalable total synthesis of (+)-spongistatin 1

Bi-mediated allylation of aldehydes in [bmim][Br]: a mechanistic investigation

Nano‐Aluminum Powder Mediated Allylation of Carbonyl Compounds in Aqueous Media

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