脒基胺硼基硅宾与单酮和二酮的氧化环加成反应研究

doi:10.6023/cjoc202212006

摘要/Abstract

合成了一种新的脒基胺硼基硅宾化合物(L)[(1,5-C₈H₁₄)B(1-Ad)N]Si (3, L=PhC(N^tBu)₂, 1-Ad=C₁₀H₁₅), 进一步研究了3和另外两种脒基胺硼基硅宾化合物(L)[(1,5-C₈H₁₄)B(2,4,6-Me₃C₆H₂)N]Si (1)和(L)[(1,5-C₈H₁₄)B(2,6-ⁱPr₂C₆H₃)N]Si (2)分别与酮类分子的反应. 化合物1和2分别与二苯甲酮发生[1+2]氧化环加成反应, 生成了SiCO-三元环化合物(L)[(1,5-C₈H₁₄)B(2,4,6-Me₃C₆H₂)N]SiOC(Ph₂) (4)和(L)[(1,5-C₈H₁₄)B(2,6-ⁱPr₂C₆H₃)N]SiOC(Ph₂) (5), 化合物3不发生反应. 化合物1~3都能与蒽酮发生[1+2]氧化环加成, 并进一步环芳香化以及CH₂基团H^–迁移, 生成硅氢蒽氧化物(L)[(1,5-C₈H₁₄)B(R)N]Si(H)OC(C₁₄H₉) [R=2,4,6-Me₃C₆H₂ (6), 2,6-ⁱPr₂C₆H₃ (7), 1-Ad (8)]. 最后探讨了化合物与二苯二乙酮的反应, 经过[1+4]氧化环加成得到SiC₂O₂-五元环化合物(L)[(1,5-C₈H₁₄)B(R)N]SiO₂C₂(Ph)₂ [R=2,4,6-Me₃C₆H₂ (9), 2,6-ⁱPr₂C₆H₃ (10), 1-Ad (11)]. 对新合成的化合物3~11进行了核磁共振波谱和元素分析表征, 并对化合物3, 5~6以及8~10进行了X射线单晶衍射结构测定, 探究了这些化合物的结构特征, 并讨论了这些反应的机理.

关键词: 官能基硅宾, 氧化环加成反应, 环芳香化Hˉ迁移反应, 含硅杂环化合物

A new amidinatoborylaminosilylene (L)[(1,5-C₈H₁₄)B(1-Ad)N]Si (3, L=PhC(NtBu)₂, 1-Ad=C₁₀H₁₅) has been synthesized. The reactions using 3 in combination of similar compounds (L)[(1,5-C₈H₁₄)B(2,4,6-Me₃C₆H₂)N]Si (1) and (L)[(1,5-C₈H₁₄)B(2,6-ⁱPr₂C₆H₃)N]Si (2) were investigated toward ketone and diketone substrates. When with Ph₂CO, no reaction occurred for 3. However 1 and 2 reacted by an oxidative [1+2]-cycloaddition to produce the SiCO-cycles (L)[(1,5-C₈H₁₄)B(2,4,6-Me₃C₆H₂)N]SiOC(Ph₂) (4) and (L)[(1,5-C₈H₁₄)B(2,6-ⁱPr₂C₆H₃)N]SiOC(Ph₂) (5), respectively. Reactions of 1~3 with anthrone yielded compounds (L)[(1,5-C₈H₁₄)B(R)N]Si(H)OC(C₁₄H₉) (R=2,4,6-Me₃C₆H₂ (6), 2,6-ⁱPr₂C₆H₃ (7), 1-Ad (8)), where the oxidative [1+2] cycloaddition followed by an H^–-migration from the CH₂ group of the central C₆-ring of anthrone under aromatization was suggested to proceed through. Furthermore, reactions of 1~3 with benzil gave SiC₂O₂-cycles as (L)[(1,5-C₈H₁₄)B(R)N]SiO₂C₂(Ph)₂ (R=2,4,6-Me₃C₆H₂ (9), 2,6-ⁱPr₂C₆H₃ (10), 1-Ad (11)) undergoing oxidative [1+4] cycloaddition. Compounds 3~11 have been characterized by NMR (¹H, ¹³C, ¹¹B, and/or ²⁹Si ) and CHN-elemental analysis, of which 3, 5~6, and 8~10 were further illustrated by X-ray crystallography. The molecule structures of these compounds were descibed and the reaction mechanisms were discussed.

Key words: functionalized silylene, oxidative cycloaddition reaction, H^–-migration under aromatization, Si-containing heterocycle

引用此文

孔德亮, 戴闻, 赵怡玲, 陈艺林, 朱红平. 脒基胺硼基硅宾与单酮和二酮的氧化环加成反应研究[J]. 有机化学, 2023, 43(5): 1843-1851.

Deliang Kong, Wen Dai, Yiling Zhao, Yilin Chen, Hongping Zhu. Study on Oxidative Cycloaddition Reactions of Amidinatoboryl-aminosilylenes toward Ketone and Diketone Molecules[J]. Chinese Journal of Organic Chemistry, 2023, 43(5): 1843-1851.

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图/表 10

图式1. 化合物3的合成

Scheme 1. Synthesis of compound 3

图1. 化合物3的晶体分子结构图及重要的键长和键角

Figure 1. X-ray crystal structure of 3 with important bond lengths and angles H atoms are omitted for clarity. Selected bond lengths (nm) and angles (°): Si(1)—N(1) 0.1866(2), Si(1)—N(2) 0.1894(2), Si(1)—N(3) 0.1804(2), B(1)—N(3) 0.1442(4); N(1)—Si(1)—N(2) 68.90(10), Si(1)—N(3)—B(1) 10.73(18).

图式2. 化合物4和5的合成

Scheme 2. Synthesis of compounds 4 and 5

图2. 化合物5的晶体分子结构图及重要的键长和键角

Figure 2. X-ray crystal structure of 5 with important bond lengths and angles H atoms are omitted for clarity. Selected bond lengths (nm) and angles (°): Si(1)—N(1) 0.17843(10), Si(1)—N(2) 0.18242(10), Si(1)—N(3) 0.19565(10), Si(1)—O(1) 0.16967(8), Si(1)—C(1) 0.18623(11), O(1)—C(1) 0.15038(13), B(1)—N(1) 0.14393(15); N(2)—Si(1)—N(3) 69.27(4), O(1)—Si(1)—C(1) 49.72(4), Si(1)—C(1)—O(1) 59.40(5), C(1)— O(1)—Si(1) 70.88(5).

图式3. 化合物6~8的合成

Scheme 3. Synthesis of compounds 6~8

图3. 化合物6的晶体分子结构图及重要的键长和键角

Figure 3. X-ray crystal structure of 6 with important bond lengths and angles H atoms except for the SiH atom are omitted for clarity. Selected bond lengths (nm) and angles (°): Si(1)—N(1) 0.17735(14), Si(1)—N(2) 0.21074(13), Si(1)—N(3) 0.18201(13), Si(1)—O(1) 0.16793(11), Si(1)—H(1) 0.1389(15), O(1)—C(1) 0.13755(19); N(2)—Si(1)—N(3) 66.31(5).

图4. 化合物8的晶体分子结构图及重要的键长和键角

Figure 4. X-ray crystal structure of 8 with important bond lengths and angles H atoms except for the SiH atom are omitted for clarity. Selected bond lengths (nm) and angles (°): Si(1)—N(1) 0.17670(10), Si(1)—N(2) 0.17516(10), Si(1)—O(1) 0.16520(8), Si(1)—H(1) 0.1371(14), O(1)—C(1) 0.13688(14), N(2)—C(15) 0.14286(15), N(3)—C(15) 0.12976(16).

图式4. 化合物9~11的合成

Scheme 4. Synthesis of compounds 9~11

图5. 化合物9的晶体分子结构图及重要的键长和键角

Figure 5. X-ray crystal structure of 9 and the important bond lengths (nm) and angles (°) H atoms are omitted for clarity. Selected bond lengths (nm) and angles (°): Si(1)—N(1) 0.19142(16), Si(1)—N(2) 0.18872(16), Si(1)—N(3) 0.17761(16), Si(1)—O(1) 0.17156(13), Si(1)—O(2) 0.17080(13), O(2)—C(33) 0.1384(2), O(1)—C(34) 0.1383(2), C(33)—C(34) 0.1339(3); N(1)—Si(1)—N(2) 68.61(7), O(1)—Si(1)—O(2) 89.23(6), C(33)—O(2)—Si(1) 112.06(11), C(34)—O(1)—Si(1) 112.28(11).

图6. 化合物10的晶体分子结构图及重要的键长和键角

Figure 6. X-ray crystal structure of 10 and the important bond lengths (nm) and angles (°) H atoms are omitted for clarity. Selected bond lengths (nm) and angles (°): Si(1)—N(1) 0.19415(10), Si(1)—N(2) 0.18621(10), Si(1)—N(3) 0.17876(10), Si(1)—O(1) 0.17223(8), Si(1)—O(2) 0.16997(8), O(1)—C(1) 0.13737(13), O(2)—C(2) 0.13941(13), C(1)—C(2) 0.13438(17); N(1)—Si(1)—N(2) 68.55(4), O(1)—Si(1)—O(2) 88.86(4), C(1)—O(1)—Si(1) 112.43(7), C(2)—O(2)—Si(1) 113.48(7).

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