DEVELOPMENT OF CARBON-CARBON BOND FORMING REACTION USING ALPHA-HYDROXYSILANE

使用α-羟基硅烷的碳-碳键形成反应的发展

• 批准号: 13680674
• 负责人: SAKAGUCHI Kazuhiko
• 金额: $ 2.11万
• 依托单位: OSAKA-CITY UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13680674/
• 关键词: α-hydroxysilane; Claisen rearrangement; [3,3] sigmatropic rearrangement; α-substituted amino acid; α-silyl cation; reverse-Brook rearrangement; tandem [1,2] shift; acid-catalyzed rearrangement; α-アシロキシシラン; ケイ素含有アミノ酸; ビニルシラン; 不斉転写

Optically active (1-hydroxy)trialkylsilane (α-hydroxysilane) group has attracted significant interests in view of its potential utility in a diastereoselective functionalization of the α-substituted vinylic CC double bond. In this report, we wish to describe: (1) highly stereoselective synthesis of vinylsilane-containing α-amino acid and α,α-disubstituted α-amino acid via a [3,3] sigmatropic rearrangement of α-acyloxysilane, and (2) acid-catalyzed rearrangement of α-hydroxysilanes.(1) A vinylsilane-containing α-amino acid and α,α-disubstituted α-amino acid having two contiguous asymmetric carbon centers at their α and β positions have been synthesized in an optically active form by ester-enolate Claisen rearrangement of the α-acyloxysilane as the key step. The present study demonstrated the potential usefulness of the α-hydroxysilyl group as an excellent chirality transferring group in the [3,3] sigmatropic rearrangement.(2) We investigated cationic rearrangement of several α-hydroxysilanes. Treatment of both optically active syn-α-hydroxycyclopropylsilane and its hydroxy group epimer (anti form) under aqueous H_2SO_4 underwent rearrangement via a common α-silyl cation intermediate to give a mixture of the ring-opened vinylsilane and two cyclopropylsilanes, the tandem [1,2]-CC bond migration products, in an optically active form. On the other hand, the acidic treatment of E- or Z-α-hydroxy alkenylsilane was each accompanied with partial racemization to give an allylic rearrangement product via a preferential syn-facial S_N2' reaction, respectively. Both α-hydroxyalkynylsilane and α-hydroxyalkylsilane were inert to the acidic condition; however, treatment of α-mesyloxyalkynylsilane under aqueous H_2SO_4 gave the mixture of rearranged products which included an optically active allene. Comparisons of the reactivities of these α-hydroxysilanes under acidic conditions are also disclosed.

光学活性的（1-羟基）三烷基硅烷（α-羟基硅烷）基团由于其在α-取代的乙烯基CC双键的非对映选择性官能化中的潜在用途而引起了极大的兴趣。本文报道：（1）通过α-酰氧基硅烷的[3，3] σ转移重排，高立体选择性地合成含乙烯基硅烷的α-氨基酸和α，α-二取代α-氨基酸;（2）α-羟基硅烷的酸催化重排。(1)以α-酰氧基硅烷的酯-烯醇化物Claisen重排为关键步骤，合成了含乙烯基硅烷的α-氨基酸和α，α-二取代的α-氨基酸，它们在α和β位上具有两个相邻的不对称碳中心。研究结果表明，α-羟基硅基在[3，3] σ迁移重排反应中具有良好的手性转移功能. (2)研究了几种α-羟基硅烷的阳离子重排反应。光学活性的顺式-α-羟基环丙基硅烷及其羟基差向异构体（反式）在H_2SO_4水溶液中通过一个共同的α-硅烷基阳离子中间体发生重排反应，得到开环的乙烯基硅烷和两个环丙基硅烷的混合物，即串联的[1，2]-CC键迁移产物。另一方面，E-和Z-α-羟基烯基硅烷的酸处理均伴随着部分外消旋，分别通过顺式S_N2'反应得到烯丙基重排产物。α-羟基炔基硅烷和α-羟基烷基硅烷对酸性条件均呈惰性，而α-甲磺酰氧基炔基硅烷在H_2SO_4水溶液中处理后，得到重排产物的混合物，其中含有光学活性的丙二烯。还公开了这些α-羟基硅烷在酸性条件下的反应性的比较。

项目成果

K.Sakaguchi, H.Suzuki, , Y.Ohfune: "Chirality Transferring [3,3] Sigmatropic Rearrangement of (1-Acyloxy-2-alkenyl)trialkylsilane. Synthesis of Optically Active Vinylsilane-Containing α-Amino Acid"Chirality. 13. 357-365 (2001)

K.Sakaguchi、H.Suzuki、Y.Ohfune：“(1-酰氧基-2-烯基)三烷基硅烷的手性转移 [3,3] Sigmatropic 重排。含光学活性乙烯基硅烷的 α-氨基酸的合成”手性 13。 .357-365 (2001)

Y.Morimoto, M.Takaishi, T.Kinoshita, K.Sakaguchi, K.Shibata: "Total synthesis and determination of the stereochemistry of 2-amino-3-cyclopropylbutanoic acid, a novel plant grouth regulator isolated from the mushroom Amanita castanopsidis Hongo"Chem. Commu

Y.Morimoto、M.Takaishi、T.Kinoshita、K.Sakaguchi、K.Shibata：“2-氨基-3-环丙基丁酸的立体化学的全合成和测定，这是一种从蘑菇 Amanita Castanopsidis Hongo 中分离出来的新型植物生长调节剂

K.Sakaguchi: "Chirality Transferring [3,3] Sigmatropic Rearrangement of (1-Acyloxy-2-alkenyl)trialkylsilane. Synthesis of Optically Active Vinylsilane-Containing α-Amino Acid"Chirality. 13. 357-365 (2001)

K. Sakaguchi：“(1-酰氧基-2-烯基)三烷基硅烷的手性转移[3,3] Sigmatropic重排。含光学活性乙烯基硅烷的α-氨基酸的合成”手性13。357-365(2001)。

K. Sakaguchi, H. Suzuki, Y. Ohfune: "Chirality Transferring [3,3] Sigmatropic Rearrangement of (1-Acyloxy-2-alkenyl)trialkylsilane. Synthesis of Optically Active Vinylsilane-Containing a-Amino Acid."Chirality. 13. 357-365 (2001)

K. Sakaguchi、H. Suzuki、Y. Ohfune：“(1-酰氧基-2-烯基)三烷基硅烷的手性转移 [3,3] Sigmatropic 重排。含 a-氨基酸的光学活性乙烯基硅烷的合成。”手性。

Y.Morimoto: "Total synthesis and determination of the stereochemistry of 2-amino-3-cyclopropylbutanoic Acid, a novel plant growth regulator isolated from the mushroom Amanta castanopsidis Hongo"Chem. Commun.. 42-43 (2002)

Y.Morimoto：“2-氨基-3-环丙基丁酸的立体化学的全合成和测定，这是一种从蘑菇 Amanta Castanopsidis Hongo 中分离出来的新型植物生长调节剂”Chem.