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CC BY-NC-ND 4.0 · Synthesis 2025; 57(15): 2320-2330
DOI: 10.1055/a-2600-0327
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Bürgenstock Special Section 2023 – Future Stars in Organic Chemistry

Rh(II)-Catalyzed Synthesis of 1,3-Diols via 5-endo-trig Cyclization of Silyl Radicals

Neha Gupta
,
Hao Deng
,
Huanyu Ding
,
Zihang Qiu
,
Constanze N. Neumann  ∗

This work was supported by the Lise-Meitner program of the Max-Planck-Gesellschaft as well as an Alexander von Humboldt-Stiftung fellowship to Z.Q. and a China Scholarship Council (CSC) PhD scholarship to H. Deng.
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Abstract

1,3-Diols, which are a frequent motif in biologically active molecules, can be prepared from readily available allylic alcohols via formal anti-Markovnikov hydration. The commonly employed hydroboration–oxidation sequence for the synthesis of terminal alcohols is challenging for allylic alcohols, and O-protection of the alcohol can be necessary. To increase atom economy, we explored the use of silane protecting groups that can be engaged in intramolecular hydrosilylation. Oxidative cleavage of the cyclized product yields the desired 1,3-diol and obviates the need for super-stoichiometric borane reagents. Based on a detailed study of O-silylation conditions, a protocol is presented that furnishes quantitative yields of a wide range of O-silylated alcohols which contain Si–H bonds for further functionalization. We show that a MOF-based Rh(II) porphyrin can furnish efficient intramolecular hydrosilylation, while the corresponding homogeneous analogue proved unreactive. Radical trapping studies suggest that silyl radicals constitute key intermediates in Rh(II)-catalyzed intramolecular hydrosilylation. Preferential 5-endo-trig versus 6-exo-trig cyclization and 5-exo-trig versus 6-endo-trig cyclization of the silyl radical intermediates led to chemoselective 1,3-diol formation for substrates containing multiple olefins.

Key words

rhodium(II) metalloradical - 1,3-diol synthesis - silyl radical - radical cyclization - MOF catalysis

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-2600-0327.
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Publication History

Received: 14 March 2025

Accepted after revision: 29 April 2025

Accepted Manuscript online:
05 May 2025

Article published online:
02 June 2025

© 2025. The Author(s). This is an open access article published by Thieme under the terms of the Creative Commons Attribution-NonDerivative-NonCommercial-License, permitting copying and reproduction so long as the original work is given appropriate credit. Contents may not be used for commercial purposes or adapted, remixed, transformed or built upon. (https://creativecommons.org/licenses/by-nc-nd/4.0/)

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