应用
频那醇硼烷是一种重要的有机中间体,同时也是关键的工业原料,广泛应用于医药、农药和染料等行业。此外,它还作为有机反应中的裂解催化剂,例如:苯甲酸促进吲哚与频那醇硼烷进行C2-H硼化反应,生成C2硼化吲哚。初步研究表明,通过频那醇硼烷的分解形成的BH3相关硼烷物种起到了催化作用。
合成方法
向5升圆底烧瓶中加入177克(1.5摩尔)频哪醇和1.6升CH2Cl2。在0℃下通过套管滴加10 M的硼烷二甲基硫醚(159 mL,0.16 mol),搅拌混合物4小时后,在室温下继续搅拌过夜。17小时后,反应混合物释放出一些气体(氢气);将反应物加热并缓慢减压至200毫米汞柱, (1.3升)得以去除。剩余液体通过套管转移到500毫升烧瓶中,在2.5小时内将压力从大气压降低至50毫米汞柱。由于持续放气,观察到粘性液体中有初始泡沫产生。此方法可提供适用于后续反应的频那醇硼烷,产率为157克,81.7%。
用途
频那醇硼烷作为硼化试剂,目前用于通过钯催化作用由2-碘代吡咯类化合物制备2-硼基吡咯类化合物。此外,它还用于通过Pd(dba)2和二-叔丁基膦苯基醚硼化芳基溴化物和氯化物。
中文名称 | 英文名称 | CAS号 | 化学式 | 分子量 |
---|---|---|---|---|
—— | DBpin | 680192-98-7 | C6H13BO2 | 128.971 |
中文名称 | 英文名称 | CAS号 | 化学式 | 分子量 |
---|---|---|---|---|
硼酸频哪醇酯 | pinacolboronic acid | 25240-59-9 | C6H13BO3 | 143.978 |
—— | 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaborolane | 67975-91-1 | C6H12BClO2 | 162.424 |
甲基硼酸频呐醇酯 | 2,4,4,5,5-pentamethyl-[1,3,2]dioxaborolane | 94242-85-0 | C7H15BO2 | 142.006 |
—— | DBpin | 680192-98-7 | C6H13BO2 | 128.971 |
—— | 2-fluoro-4,4,5,5-tetramethyl-1,3,2-dioxaborolane | 897955-33-8 | C6H12BFO2 | 145.969 |
2-甲氧基-4,4,5,5-四甲基-1,3,2-二氧硼戊环 | 2-methoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane | 1195-66-0 | C7H15BO3 | 158.005 |
乙氧基硼酸频哪醇酯 | 2-ethoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane | 1126-93-8 | C8H17BO3 | 172.032 |
—— | 2-isobutoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane | 94584-18-6 | C10H21BO3 | 200.086 |
—— | 4,4,5,5-tetramethyl-2-propoxy-1,3,2-dioxaborolane | 1130-16-1 | C9H19BO3 | 186.059 |
—— | 2-(tert-butoxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane | 94647-81-1 | C10H21BO3 | 200.086 |
—— | 2-(sec-butoxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane | 94647-82-2 | C10H21BO3 | 200.086 |
异丙醇频哪醇硼酸酯 | 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane | 61676-62-8 | C9H19BO3 | 186.059 |
—— | 2-(but-3-en-1-yloxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane | —— | C10H19BO3 | 198.07 |
—— | <1,3-Dimethyl-butyl>-<1,1,2,2-tetramethyl-ethylen>-borat | 94981-94-9 | C12H25BO3 | 228.14 |
乙基硼酸频那醇酯 | ethylboronic acid pinacol ester | 82954-89-0 | C8H17BO2 | 156.033 |
碘甲基硼酸频哪醇酯 | 2-(iodomethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane | 70557-99-2 | C7H14BIO2 | 267.902 |
乙烯基硼酸频哪醇酯 | pinacol vinylboronate | 75927-49-0 | C8H15BO2 | 154.017 |
—— | isopropenyl pinacol boronic ester | 960048-87-7 | C9H17BO3 | 184.043 |
—— | bis(pinacolato)diborane | 10221-56-4 | C12H24B2O5 | 269.942 |
硼酸环乙醇频哪醇酯 | 2-(cyclohexyloxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane | 96649-78-4 | C12H23BO3 | 226.124 |
1-丙硼酸频哪醇酯 | 4,4,5,5-tetramethyl-2-propyl-1,3,2-dioxaborolane | 67562-19-0 | C9H19BO2 | 170.06 |
2-异丙基硼酸频那醇酯 | 2-isopropyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane | 76347-13-2 | C9H19BO2 | 170.06 |
Macrocycles of the bisbibenzyl-type are natural products that are found exclusively in bryophytes (liverworts). The molecular framework of the subtype “isoplagiochin” is of substantial structural interest because of the chirality of the entire molecule, which arises from two biaryl axes in combination with two helical two-carbon units in a cyclic arrangement. From a structural as well as a synthetic point of view we report on the total synthesis of compounds which possess more rigid two-carbon biaryl bridges like stilbene (