C–C Bond Formation at an Aluminacyclopropane

IF 2.9 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Organometallics Pub Date : 2025-07-21 DOI:10.1021/acs.organomet.5c00169

Andrea O’Reilly, J. Robin Fulton* and Martyn P. Coles*,

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引用次数: 0

Abstract

The reactivity of the aluminacyclopropane compound K[Al(NON)(η²-C₂H₄)] (NON = κN,N’-[O(SiMe₂NDipp)₂]^2–; Dipp = 2,6-iPr₂C₆H₃) toward isocyanides R–NC (R = Cy, Ad, tBu; Cy = cyclohexyl, Ad = 1-adamantyl) and benzophenone is described. All reactions proceed via insertion of the substrate into an Al–C bond of the aluminacycle, with C–C bond formation leading to ring-expanded products. With isocyanide substrates, either monoinsertion (R = Cy, Ad, tBu) to afford the four-membered aluminacyclobuta-1-imine ring, or double insertion (R = tBu) to form an aluminacyclopenta-1,2-diimine ring is observed. The reaction with benzophenone affords the corresponding insertion product that incorporates the C═O functionality to form an expanded five-membered AlOC₃ ’alumina-tetrahydrofuran’ ring. The NON-ligand of this product undergoes a thermally induced, intramolecular 1,3-silyl retro-Brook rearrangement to afford the corresponding “Al(NNO)” product ([NNO]^2– = κN,O-[N(Dipp)SiMe₂N(Dipp)SiMe₂O]^2–).

Abstract Image

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铝环丙烷的C-C键形成

铝环丙烷化合物K[Al(NON)(η - 2- c2h4)] (NON = κN,N ' -[O(SiMe2NDipp)2]2 -的反应性Dipp = 2,6- ipr2c6h3)对异氰化物R - nc (R = Cy, Ad, tBu；Cy =环己基，Ad = 1-金刚烷基)和二苯甲酮。所有的反应都是通过将底物插入铝环的Al-C键进行的，C-C键的形成导致环膨胀产物。对于异氰化物底物，单插入（R = Cy, Ad, tBu）形成四元铝无环戊-1-亚胺环，或双插入（R = tBu）形成铝无环戊-1,2-二亚胺环。与二苯甲酮反应产生相应的插入产物，该插入产物包含C = O功能，形成扩展的五元AlOC3 ‘氧化铝-四氢呋喃’环。该产物的非配体经过热诱导的分子内1,3-硅基逆转录布鲁克重排生成相应的“Al（NNO）”产物([NNO]2 - = κN,O-[N（Dipp)SiMe2N(Dipp)SiMe2O]2 -）。

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来源期刊

Organometallics 化学-无机化学与核化学

CiteScore

5.60

自引率

7.10%

发文量

382

审稿时长

1.7 months

期刊介绍： Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.