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Amine-directed hydroboration: scope and limitations.

ABSTRACT: Iodine activation induces intramolecular hydroboration of homoallylic and bis-homoallylic amine boranes with good to excellent control of regiochemistry compared to control experiments using excess THF*BH 3. Deuterium labeling and other evidence confirm that the iodine-induced hydroboration reaction of homoallylic amine boranes occurs via an intramolecular mechanism equivalent to the classical 4-center process and without competing retro-hydroboration. Longer carbon chain tethers result in lower regioselectivity, whereas the shorter tether in allylic amines results in a switch to dominant intermolecular hydroboration. Regioselectivity in THF*BH 3 control experiments is higher for the allylic amine boranes compared to the iodine activation experiments, whereas the reverse is true for homoallylic amine borane activation.

SUBMITTER: Scheideman M

PROVIDER: S-EPMC2646876 | biostudies-other | 2008 Jul

REPOSITORIES: biostudies-other

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Amine-directed hydroboration: scope and limitations.

Scheideman Matthew M Wang Guoqiang G Vedejs Edwin E

Journal of the American Chemical Society 20080613 27

Iodine activation induces intramolecular hydroboration of homoallylic and bis-homoallylic amine boranes with good to excellent control of regiochemistry compared to control experiments using excess THF*BH 3. Deuterium labeling and other evidence confirm that the iodine-induced hydroboration reaction of homoallylic amine boranes occurs via an intramolecular mechanism equivalent to the classical 4-center process and without competing retro-hydroboration. Longer carbon chain tethers result in lower ...[more]

PMID: 18549217

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Project description:The aromaticity of cyclic 4nπ-electron molecules in their first ππ* triplet state (T1), labeled Baird aromaticity, has gained growing attention in the past decade. Here we explore computationally the limitations of T1 state Baird aromaticity in macrocyclic compounds, [n]CM's, which are cyclic oligomers of four different monocycles (M = p-phenylene (PP), 2,5-linked furan (FU), 1,4-linked cyclohexa-1,3-diene (CHD), and 1,4-linked cyclopentadiene (CPD)). We strive for conclusions that are general for various DFT functionals, although for macrocycles with up to 20 π-electrons in their main conjugation paths we find that for their T1 states single-point energies at both canonical UCCSD(T) and approximative DLPNO-UCCSD(T) levels are lowest when based on UB3LYP over UM06-2X and UCAM-B3LYP geometries. This finding is in contrast to what has earlier been observed for the electronic ground state of expanded porphyrins. Yet, irrespective of functional, macrocycles with 2,5-linked furans ([n]CFU's) retain Baird aromaticity until larger n than those composed of the other three monocycles. Also, when based on geometric, electronic and energetic aspects of aromaticity, a 3[n]CFU with a specific n is more strongly Baird-aromatic than the analogous 3[n]CPP while the magnetic indices tell the opposite. To construct large T1 state Baird-aromatic [n]CM's, the design should be such that the T1 state Baird aromaticity of the macrocyclic perimeter dominates over a situation with local closed-shell Hückel aromaticity of one or a few monocycles and semilocalized triplet diradical character. Monomers with lower Hückel aromaticity in S0 than benzene (e.g., furan) that do not impose steric congestion are preferred. Structural confinement imposed by, e.g., methylene bridges is also an approach to larger Baird-aromatic macrocycles. Finally, by using the Zilberg-Haas description of T1 state aromaticity, we reveal the analogy to the Hückel aromaticity of the corresponding closed-shell dications yet observe stronger Hückel aromaticity in the macrocyclic dications than Baird aromaticity in the T1 states of the neutral macrocycles.

Dataset Information

Amine-directed hydroboration: scope and limitations.

Publications

Amine-directed hydroboration: scope and limitations.

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