O-Carboranylene versus Phenylene Backbones in Cyclization Reactions of 1,2 Diketones with Hydrosilanes

Kuldeep Jaiswal; Karina Chulsky; Mark Gandelman; Roman Dobrovetsky

doi:10.1021/acs.organomet.0c00208

O-Carboranylene versus Phenylene Backbones in Cyclization Reactions of 1,2 Diketones with Hydrosilanes

Kuldeep Jaiswal, Karina Chulsky, Mark Gandelman, Roman Dobrovetsky

Research output: Contribution to journal › Article › peer-review

1 Scopus citations

Abstract

The difference in reactivity of 1,2-dibenzoyl-o-carborane (2) and its analogue with an aromatic backbone and two C₆F₅electron withdrawing groups, C₆H₄(CO(C₆F₅))₂(5), in cyclization reactions with R₃SiH (R = Et, Ph (a)) with or without a catalytic amount of B(C₆F₅)₃was studied. In contrast to the reaction of 2 with R₃SiH, which directly leads to the cyclic hydrofurane products 3 and 4, 5 and R₃SiH do not react without a catalytic amount of B(C₆F₅)₃. However, in the presence of a catalytic amount of B(C₆F₅)₃, 5 reacts with R₃SiH forming through hydrofurane-type products 9, 9a, isobenzofuran 6. 2, on the other hand, reacts with R₃SiH in the presence of a catalytic amount of B(C₆F₅)₃giving stable products 10, 10a. 10, 10a in the presence of B(C₆F₅)₃transform over time to a mixture of diastereomers 3′, 3a′. The mechanisms leading to these reactions are proposed on the basis of experimental and computational investigation.

Original language	English
Pages (from-to)	4232-4237
Number of pages	6
Journal	Organometallics
Volume	39
Issue number	23
DOIs	https://doi.org/10.1021/acs.organomet.0c00208
State	Published - 14 Dec 2020
Externally published	Yes

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© 2020 American Chemical Society. All rights reserved.

Funding

This work was supported by the Israel Ministry of Science Technology & Space, Grant 65692, and the Israeli Science Foundation, Grant 237/18.

Funders	Funder number
Ministry of Science, Technology and Space	65692
Israel Science Foundation	237/18

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title = "O-Carboranylene versus Phenylene Backbones in Cyclization Reactions of 1,2 Diketones with Hydrosilanes",

abstract = "The difference in reactivity of 1,2-dibenzoyl-o-carborane (2) and its analogue with an aromatic backbone and two C6F5electron withdrawing groups, C6H4(CO(C6F5))2(5), in cyclization reactions with R3SiH (R = Et, Ph (a)) with or without a catalytic amount of B(C6F5)3was studied. In contrast to the reaction of 2 with R3SiH, which directly leads to the cyclic hydrofurane products 3 and 4, 5 and R3SiH do not react without a catalytic amount of B(C6F5)3. However, in the presence of a catalytic amount of B(C6F5)3, 5 reacts with R3SiH forming through hydrofurane-type products 9, 9a, isobenzofuran 6. 2, on the other hand, reacts with R3SiH in the presence of a catalytic amount of B(C6F5)3giving stable products 10, 10a. 10, 10a in the presence of B(C6F5)3transform over time to a mixture of diastereomers 3′, 3a′. The mechanisms leading to these reactions are proposed on the basis of experimental and computational investigation.",

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AU - Dobrovetsky, Roman

PY - 2020/12/14

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N2 - The difference in reactivity of 1,2-dibenzoyl-o-carborane (2) and its analogue with an aromatic backbone and two C6F5electron withdrawing groups, C6H4(CO(C6F5))2(5), in cyclization reactions with R3SiH (R = Et, Ph (a)) with or without a catalytic amount of B(C6F5)3was studied. In contrast to the reaction of 2 with R3SiH, which directly leads to the cyclic hydrofurane products 3 and 4, 5 and R3SiH do not react without a catalytic amount of B(C6F5)3. However, in the presence of a catalytic amount of B(C6F5)3, 5 reacts with R3SiH forming through hydrofurane-type products 9, 9a, isobenzofuran 6. 2, on the other hand, reacts with R3SiH in the presence of a catalytic amount of B(C6F5)3giving stable products 10, 10a. 10, 10a in the presence of B(C6F5)3transform over time to a mixture of diastereomers 3′, 3a′. The mechanisms leading to these reactions are proposed on the basis of experimental and computational investigation.

AB - The difference in reactivity of 1,2-dibenzoyl-o-carborane (2) and its analogue with an aromatic backbone and two C6F5electron withdrawing groups, C6H4(CO(C6F5))2(5), in cyclization reactions with R3SiH (R = Et, Ph (a)) with or without a catalytic amount of B(C6F5)3was studied. In contrast to the reaction of 2 with R3SiH, which directly leads to the cyclic hydrofurane products 3 and 4, 5 and R3SiH do not react without a catalytic amount of B(C6F5)3. However, in the presence of a catalytic amount of B(C6F5)3, 5 reacts with R3SiH forming through hydrofurane-type products 9, 9a, isobenzofuran 6. 2, on the other hand, reacts with R3SiH in the presence of a catalytic amount of B(C6F5)3giving stable products 10, 10a. 10, 10a in the presence of B(C6F5)3transform over time to a mixture of diastereomers 3′, 3a′. The mechanisms leading to these reactions are proposed on the basis of experimental and computational investigation.

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O-Carboranylene versus Phenylene Backbones in Cyclization Reactions of 1,2 Diketones with Hydrosilanes

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