CAS: 85134-98-1; Methoxybis((1R,2S,3R,5R)-2,6,6-Trimethylbicyclo[3.1.1]Heptan-3-yl)Borane

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CAS号67-56-1 甲醇 | CAS号21932-54-7 (-)-二异松蒎基硼烷 | CAS号7785-70-8 蒎烯 | CAS号1196-00-5 (-)-异松蒎醇 | CAS号197230-20-9 (R)-7-azido-1-h...

甲醇,Pinene置于tert-Butylbis(2-Methoxyethyl)Amine-Borane体系中,用 四氢呋喃 作为反应溶剂,化学反应 24.0H,反应生成 (-)-B-甲氧基二异松莰基硼烷,Dimethoxy-(2,6,6-Trimethyl-3-Bicyclo[3.1.1]Heptanyl)Borane
参考文献:Molecular Addition Compounds. 15. Synthesis,Hydroboration,And Reduction Studies Of New,Highly Reactive Tert-Butyldialkylamine−borane Adducts
标题:Molecular Addition Compounds. 15. Synthesis,Hydroboration,And Reduction Studies Of New,Highly Reactive Tert-Butyldialkylamine−borane Adducts
摘要:Two Series Of Tert-Butyldialkylamines Have Been Prepared And Examined For Borane Complexation. The Complexing Ability Of Each Amine In The Two Series Examined Decreases In The Order Shown. First Series: T-Bun(Ch2Ch2)(2)O 1A > T-Bunet2 Ib > T-Bunpr(2)(N)1C > T-Bun(Ch2Ch2Ome)(2) Id Much Greater Than T-Bunbu2I Le. Second Series: T-(Bunbume)-Me-I 2A > T-(Bunprme)-Me-I 2B > T-(Bunbuet)-Et-I 2C > T-(Bunbuprn)-Pr-I 2D Much Greater Than T-(Bunpret)-Et-I 2E. The Reactivity Of The Corresponding Borane Adducts Toward 1-octene Increases In The Reverse Order. The Following Amines Form Highly Reactive Liquid Borane Adducts Hydroborating 1-octene In Tetrahydrofuran At Room Temperature In Less Than 1 H: T-Bun(Ch2Ch2Ome)(2),T-(Bunbuet)-Et-I,And T-(Bunprme)-Me-I. The Limit Of Borane Complexation Among The Amines Examined Is Reached For T-Bunbu2I Exchanging Borane Neither With Ems Nor With Bh3-Thf. Among The Various Borane Adducts Prepared,The More Promising Borane Adducts,T-Bu(Ch3och2Ch2)(2)N-Bh3 (7),T-(Bumeprn)-N-I-Bh3 (8),And T-(Buetbun)-N-I-Bh3 (9),Were Selected For Complete Hydroboration And Reduction Studies. Hydroboration Studies With The New,Highly Reactive Trialkylamine-Borane Adducts 7-9 And Representative Olefins,Such As L-Hexene,Styrene,Beta-Pinene,Cyclopentene,Norbornene,Cyclohexene,2-Methyl-2-Butene,Alpha-Pinene,And 2,3-Dimethyl-2-Butene,In Tetrahydrofuran,Dioxane,Tert-Butyl Methyl Ether,N-Pentane,And Dichloromethane,At Room Temperature (22 +/-3 Degrees C) Were Carried Out. The Reactions Are Faster In Dioxane,Requiring 1-2 H For The Hydroboration Of Simple,Unhindered Olefins To The Trialkylborane Stage. Moderately Hindered Olefins,Such As Cyclohexene And 2-Methyl-2-Butene,Give The Corresponding Dialkylboranes Rapidly,With Further Slow Hydroboration. However,The More Hindered Olefins,Alpha-Pinene And 2,3-Dimethyl-2-Butene,Give Stable Monoalkylboranes Very Rapidly,With Further Hydroboration Proceeding Relatively Slowly. The Hydroborations Can Also Be Carried Out Conveniently In Other Solvents,Such As Thf,Tert-Butyl Methyl Ether,And N-Pentane. A Significant; Rate Retardation Is Observed In Dichloromethane. Regioselectivity Studies Of L-Hexene And Styrene Using These Amine-Borane Adducts Show Selectivities Similar To That Of Bh3-Thf. The Rates And Stoichiometry Of The Reaction Of T-Bumeprin-Bh3 In Tetrahydrofuran With Selected Organic Compounds Containing Representative Functional Groups Were Also Examined At Room Temperature. The Reductions Of Esters,Amides,And Nitriles,Which Exhibit A Sluggish Reaction At Room Temperature,Proceed Readily Under Reflux Conditions In Tetrahydrofuran And Dioxane And Without Solvent (At 85-90 Degrees C). The Carrier Amines Can Be Recovered By Simple Acid-Base Manipulations In Good Yield And Readily Recycled To Make The Borane Adducts.
DOI:10.1021/jo990379B