Study on Oxidative Cycloaddition Reactions of Amidinatoboryl-aminosilylenes toward Ketone and Diketone Molecules

doi:10.6023/cjoc202212006

Chinese Journal of Organic Chemistry ›› 2023, Vol. 43 ›› Issue (5): 1843-1851.DOI: 10.6023/cjoc202212006 Previous Articles Next Articles

Special Issue: 有机硼化学专辑

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脒基胺硼基硅宾与单酮和二酮的氧化环加成反应研究

孔德亮, 戴闻, 赵怡玲, 陈艺林, 朱红平^*()

厦门大学化学化工学院固体表面物理化学国家重点实验室厦门 361005

收稿日期:2022-12-06 修回日期:2023-02-23 发布日期:2023-03-07
通讯作者: 朱红平
基金资助:
国家自然科学基金(21972112); 国家自然科学基金(22078274)

Study on Oxidative Cycloaddition Reactions of Amidinatoboryl-aminosilylenes toward Ketone and Diketone Molecules

Deliang Kong, Wen Dai, Yiling Zhao, Yilin Chen, Hongping Zhu()

State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005

Received:2022-12-06 Revised:2023-02-23 Published:2023-03-07
Contact: Hongping Zhu
Supported by:
National Natural Science Foundation of China(21972112); National Natural Science Foundation of China(22078274)

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Abstract

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

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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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Fig. & Tab. 10

Scheme 1. Synthesis of compound 3

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).

Scheme 2. Synthesis of compounds 4 and 5

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).

Scheme 3. Synthesis of compounds 6~8

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).

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).

Scheme 4. Synthesis of compounds 9~11

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).

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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脒基胺硼基硅宾与单酮和二酮的氧化环加成反应研究

Study on Oxidative Cycloaddition Reactions of Amidinatoboryl-aminosilylenes toward Ketone and Diketone Molecules

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