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Alkali metal complexes as efficient catalysts for hydroboration and cyanosilylation of carbonyl compounds†
Dalton Transactions ( IF 3.5 ) Pub Date : 2018-07-17 00:00:00 , DOI: 10.1039/c8dt02032a Adimulam Harinath 1, 2, 3, 4 , Jayeeta Bhattacharjee 1, 2, 3, 4 , Hari Pada Nayek 4, 5, 6 , Tarun K. Panda 1, 2, 3, 4
Dalton Transactions ( IF 3.5 ) Pub Date : 2018-07-17 00:00:00 , DOI: 10.1039/c8dt02032a Adimulam Harinath 1, 2, 3, 4 , Jayeeta Bhattacharjee 1, 2, 3, 4 , Hari Pada Nayek 4, 5, 6 , Tarun K. Panda 1, 2, 3, 4
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We report here reactions between the N-adamantyliminopyrolyl ligand 2-(AdN![[double bond, length as m-dash]](https://www.rsc.org/images/entities/char_e001.gif)
CH)–C4H3NH (L–H) and alkali metal hexamethyldisilazides [MN(SiMe3)2] (M = Li, Na and K) to afford the dimeric [{2-(AdNCH)–C4H3NLi(THF)}2] (1), [{2-(AdNCH)–C4H3N}{Na(THF)1.5}2] (2) and polymeric [{2-(AdNCH)–C4H3NK(THF)}n] (3) complexes at ambient temperature. A one-pot reaction between L–H, [KN(SiMe3)2] and alkaline earth metal diiodide (AeI2) in a 2 : 2 : 1 molar ratio, which resulted in the formation of a heteroleptic Ae metal complex [κ2-{2-(AdNCH)–C4H3N}2Ae(THF)2] [Ae = Mg (4), Ca (5)], is also reported. The solid-state structures of complexes 1, 3 and 4 were established through single-crystal X-ray diffraction analysis. The alkali and alkaline earth metal complexes 1–5 were utilised as precatalysts for the catalytic hydroboration of pinacolborane (HBpin) with aldehydes and ketones, and potassium complex 3 was identified as a competent catalyst under mild conditions. Additionally, cyanosilylation of carbonyl compounds was explored with trimethylsilyl cyanide and aldehydes/ketones, using the alkali metal precatalyst 3 under mild conditions. In both catalytic processes, the potassium catalyst 3 exhibited high tolerance towards a number of functional groups.
中文翻译：
碱金属配合物可作为羰基化合物加氢硼化和氰基硅烷化的有效催化剂†
我们在这里报告N-金刚烷基吡咯基配体2-（AdN CH）–C 4 H 3 NH（L–H）与碱金属六甲基二硅叠氮化物[MN（SiMe 3）2 ]（M = Li，Na和K）之间的反应二聚体[{2-（AdN CH）–C 4 H 3 NLi（THF）} 2 ]（1），[{2-（AdN CH）–C 4 H 3 N} {Na（THF）1.5 } 2 ] （2）和聚合的[{2-（AdN CH）–C 4 H 3 NK（THF）} n ]（3）在环境温度下的配合物。L–H，[KN（SiMe 3）2 ]与碱土金属二碘化物（AeI 2）之间以2：2：1的摩尔比进行一锅反应，导致形成杂配Ae金属络合物[κ]还报告了2- {2-（AdN CH）–C 4 H 3 N} 2 Ae（THF）2 ] [Ae = Mg（4），Ca（5）]。复合物的固态结构1，3和4通过单晶X射线衍射分析来建立。碱金属和碱土金属配合物1-5被用作对频哪醇硼烷（HBpin）与醛和酮进行催化加氢硼化的前催化剂，而钾配合物3被确定为在温和条件下的有效催化剂。另外，在适度的条件下，使用碱金属预催化剂3，用三甲基甲硅烷基氰化物和醛/酮探索了羰基化合物的氰基硅烷化反应。在两种催化方法中，钾催化剂3均表现出对许多官能团的高耐受性。
更新日期：2018-07-17
CH)–C4H3NH (L–H) and alkali metal hexamethyldisilazides [MN(SiMe3)2] (M = Li, Na and K) to afford the dimeric [{2-(AdNCH)–C4H3NLi(THF)}2] (1), [{2-(AdNCH)–C4H3N}{Na(THF)1.5}2] (2) and polymeric [{2-(AdNCH)–C4H3NK(THF)}n] (3) complexes at ambient temperature. A one-pot reaction between L–H, [KN(SiMe3)2] and alkaline earth metal diiodide (AeI2) in a 2 : 2 : 1 molar ratio, which resulted in the formation of a heteroleptic Ae metal complex [κ2-{2-(AdNCH)–C4H3N}2Ae(THF)2] [Ae = Mg (4), Ca (5)], is also reported. The solid-state structures of complexes 1, 3 and 4 were established through single-crystal X-ray diffraction analysis. The alkali and alkaline earth metal complexes 1–5 were utilised as precatalysts for the catalytic hydroboration of pinacolborane (HBpin) with aldehydes and ketones, and potassium complex 3 was identified as a competent catalyst under mild conditions. Additionally, cyanosilylation of carbonyl compounds was explored with trimethylsilyl cyanide and aldehydes/ketones, using the alkali metal precatalyst 3 under mild conditions. In both catalytic processes, the potassium catalyst 3 exhibited high tolerance towards a number of functional groups.
中文翻译：
碱金属配合物可作为羰基化合物加氢硼化和氰基硅烷化的有效催化剂†
我们在这里报告N-金刚烷基吡咯
基配体2-（AdN CH）–C 4 H 3 NH（L–H）与碱金属六甲基二硅叠氮化物[MN（SiMe 3）2 ]（M = Li，Na和K）之间的反应二聚体[{2-（AdN CH）–C 4 H 3 NLi（THF）} 2 ]（1），[{2-（AdN CH）–C 4 H 3 N} {Na（THF）1.5 } 2 ] （2）和聚合的[{2-（AdN CH）–C 4 H 3 NK（THF）} n ]（3）在环境温度下的配合物。L–H，[KN（SiMe 3）2 ]与碱土金属二碘化物（AeI 2）之间以2：2：1的摩尔比进行一锅反应，导致形成杂配Ae金属络合物[κ]还报告了2- {2-（AdN CH）–C 4 H 3 N} 2 Ae（THF）2 ] [Ae = Mg（4），Ca（5）]。复合物的固态结构1，3和4通过单晶X射线衍射分析来建立。碱金属和碱土金属配合物1-5被用作对频哪醇硼烷（HBpin）与醛和酮进行催化加氢硼化的前催化剂，而钾配合物3被确定为在温和条件下的有效催化剂。另外，在适度的条件下，使用碱金属预催化剂3，用三甲基甲硅烷基氰化物和醛/酮探索了羰基化合物的氰基硅烷化反应。在两种催化方法中，钾催化剂3均表现出对许多官能团的高耐受性。
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