金属卡宾参与的对映选择性去对称化反应研究进展

doi:10.6023/cjoc202206041

摘要/Abstract

金属卡宾在有机合成中具有非常重要的应用, 其不同的活性可以发生形式多样的化学反应. 以金属卡宾的反应类型分类, 介绍了金属卡宾参与的去对称化C—H插入反应、Buchner反应、Si—H插入反应和B—H插入反应. 在手性铑、钌、铜等催化剂的催化下, 反应可高对映选择性地合成手性碳环化合物、杂环化合物、有机硅化合物和有机硼化合物, 极大地丰富了不对称合成化学的发展.

关键词: 重氮化合物, 金属卡宾, 去对称化, 不对称合成

Metal carbenes have been widely applied in organic synthesis, and they can undergo a variety of chemical transformations due to their versatile reactivities. In this review, the desymmetrization of C—H insertion reaction, Buchner reaction, Si—H insertion reaction and B—H insertion reaction involving metal carbenes is introduced according to the different reaction types of metal carbenes. Under the catalysis of chiral rhodium, ruthenium and copper catalysts, chiral carbocycles, heterocycles, organosilicons and organoborons can be obtained with high enantioselectivity, which greatly enriches the development of asymmetric synthetic chemistry.

Key words: diazo compounds, metal carbene, desymmetrization, aymmetric synthesis

引用此文

滕明瑜, 韩涛, 黄恩和, 叶龙武. 金属卡宾参与的对映选择性去对称化反应研究进展[J]. 有机化学, 2022, 42(10): 3295-3301.

Ming-Yu Teng, Tao Han, En-He Huang, Long-Wu Ye. Research Progress on Enantioselective Desymmetrization Reactions Involving Metal Carbenes[J]. Chinese Journal of Organic Chemistry, 2022, 42(10): 3295-3301.

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图/表 16

图式1. 重氮化合物生成金属卡宾参与的反应

Scheme 1. Reactions involving metal carbenes from diazo com- pounds

图式2. 对映选择性去对称化反应合成手性化合物

Scheme 2. Synthesis of chiral compounds from enantioselective desymmetrization reactions

图式3. 铑催化重氮酯化合物的去对称化C—H插入反应

Scheme 3. Rh-catalyzed desymmetrization of C—H insertion reaction of diazoacetates

图式4. 铑催化环烷基重氮酯化合物的去对称化C—H插入反应

Scheme 4. Rh-catalyzed desymmetrization of C—H insertion reaction of cycloalkyl diazoacetates

图式5. 铑催化α-烷基-α-重氮酯化合物的去对称化C—H插入反应

Scheme 5. Rh-catalyzed desymmetrization of C—H insertion reaction of α-alkyl-α-diazoesters

图式6. 铑催化α-重氮-β-氧代砜化合物的去对称化C—H插入反应

Scheme 6. Rh-catalyzed desymmetrization of C—H insertion reaction of α-diazo-β-oxosulfones

图式7. 铜催化内消旋氧杂双环重氮羰基化合物的去对称化 C—H插入反应

Scheme 7. Copper-catalyzed desymmetrization of C—H insertion reaction of meso-oxabicyclo diazoketones

图式8. 铜催化2-砜基-2-重氮酰胺化合物的去对称化C—H插入反应

Scheme 8. Copper-catalyzed desymmetrization of C—H insertion reaction of 2-sulfonyl-2-diazoacetamides

图式9. 铜催化α-重氮-β-氧代砜化合物的去对称化C—H插入反应

Scheme 9. Copper-catalyzed desymmetrization of C—H insertion reaction of α-diazo-β-oxosulfones

图式10. 铑催化δ,δ-二芳基重氮羰基酯化合物的去对称化Buchner反应

Scheme 10. Rh-catalyzed desymmetrization of Buchner reaction of δ,δ-diaryl diazoacetoacetates

图式11. 钌催化重氮酰胺化合物的去对称化Buchner反应

Scheme 11. Ru-catalyzed desymmetrization of Buchner reaction of diazoacetamides

图式12. 铑催化α-氰基-α-重氮酰胺化合物的去对称化Buchner反应

Scheme 12. Rh-catalyzed desymmetrization of Buchner reaction of α-cyano-α-diazoacetamides

图式13. 铱催化重氮酯化合物的去对称化Si—H插入反应

Scheme 13. Ir-catalyzed desymmetrization of Si—H insertion reaction of diazoacetates

图式14. 钌催化重氮酯化合物的去对称化Si—H插入反应

Scheme 14. Ru-catalyzed desymmetrization of Si—H insertion reaction of diazoacetates

图式15. 铑催化二芳基重氮化合物的去对称化Si—H插入反应

Scheme 15. Rh-catalyzed desymmetrization of Si—H insertion reaction of diaryl-diazo compounds

图式16. 铜催化重氮化合物的去对称化B—H插入反应

Scheme 16. Cu-catalyzed desymmetrization of B—H insertion reaction of diazo compounds

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