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. 2024 Nov 15;4(12):4927-4933.
doi: 10.1021/jacsau.4c00907. eCollection 2024 Dec 23.

Transition-Metal-Free Thioboration of Terminal Alkynes

Taro Matsuyama  1 , Hiroshi Ishida  1 , Chao Wang  2 , Kazunori Miyamoto  1   3 , Masaya Nakajima  1 , Naoyuki Toriumi  1 , Yuki Nagashima  1 , Masanobu Uchiyama  1   4
Affiliations

Transition-Metal-Free Thioboration of Terminal Alkynes

Taro Matsuyama et al. JACS Au. .

Abstract

We present a new type of elementoboration reaction, the thioboration of terminal alkynes. This method enables highly controllable regio-/stereo-/chemoselective cis- and trans-thioboration on demand, affording synthetically versatile and densely functionalized vinyl boron/vinyl sulfide derivatives in a straightforward manner without the need for a transition-metal catalyst.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Background of elementoboration chemistry.
Scheme 1
Scheme 1. Transformations of cis- and trans-Thioboration Products
(a) 4-Iodoanisole (2.0 equiv), Pd(OAc)2 (10 mol %), SPhos (20 mol %), CsOH·H2O (3.0 equiv), THF, rt, 48 h, under argon. (b) CuBr2 (3.0 equiv), MeOH/H2O, 80 °C, 30 min. Starting materials were totally consumed, and in cases where product yields were lower than expected, this might be explained by protodeboration of the starting materials or an intermolecular aldol reaction or protodesilylation.
Figure 2
Figure 2
Mechanistic studies and proposed mechanisms. aCalculation was performed at the M06-2X/6-31+G(d,p) level. Gibbs free energies relative to 3v are shown in parentheses (kcal mol–1). bCalculation was performed at the M06-2X/6-31+G(d,p) level. Gibbs free energies relative to ii are shown in parentheses (kcal mol–1).
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References

    1. Negishi E. Magical Power of Transition Metals: Past, Present, and Future. Angew. Chem., Int. Ed. 2011, 50, 6738–6764. 10.1002/anie.201101380. - DOI - PubMed
    2. Yoshida H. Borylation of Alkynes under Base/Coinage Metal Catalysis: Some Recent Developments. ACS Catal. 2016, 6, 1799–1811. 10.1021/acscatal.5b02973. - DOI
    3. Ansell M. B.; Navarro O.; Spencer J. Transition metal catalyzed element–element’ additions to alkynes. Coord. Chem. Rev. 2017, 336, 54–77. 10.1016/j.ccr.2017.01.003. - DOI
    4. Whyte A.; Torelli A.; Mirabi B.; Zhang A.; Lautens M. Copper-Catalyzed Borylative Difunctionalization of π-Systems. ACS Catal. 2020, 10, 11578–11622. 10.1021/acscatal.0c02758. - DOI
    5. Altarejos J.; Valero A.; Manzano R.; Carreras J. Synthesis of Tri- and Tetrasubstituted Alkenyl Boronates from Alkynes. Eur. J. Org Chem. 2022, 2022, e20220052110.1002/ejoc.202200521. - DOI

    1. Initial reports (B–H):

    2. Brown H. C.; Rao B. C. S. A New Technique for the Conversion of Olefins into Organoboranes and Related Alcohols. J. Am. Chem. Soc. 1956, 78, 5694–5695. 10.1021/ja01602a063. - DOI
    3. Brown H. C.; Chen J. Hydroboration. 57. Hydroboration with 9-borabicyclo[3.3.1]nonane of alkenes containing representative functional groups. J. Org. Chem. 1981, 46, 3978–3988. 10.1021/jo00333a009. - DOI

    1. Recent representative reviews (B–H):

    2. Rej S.; Das A.; Panda T. K. Overview of Regioselective and Stereoselective Catalytic Hydroboration of Alkynes. Adv. Synth. Catal. 2021, 363, 4818–4840. 10.1002/adsc.202100950. - DOI
    3. Magre M.; Szewczyk M.; Rueping M. s-Block Metal Catalysts for the Hydroboration of Unsaturated Bonds. Chem. Rev. 2022, 122, 8261–8312. 10.1021/acs.chemrev.1c00641. - DOI - PMC - PubMed
    1. Kirschner S.; Yuan K.; Ingleson M. J.; Haloboration: scope, mechanism and utility. New J. Chem. 2021, 45, 14855–14868. 10.1039/d0nj02908d. - DOI - PMC - PubMed

    1. Early reports (B–Halogen):

    2. Lappert M. F.; Prokai B. Chloroboration and Allied Reactions of Unsaturated Compounds II. Haloboration and Phenylboration of Acetylenes; and the Preparation of Some Alkynylboranes. J. Organomet. Chem. 1964, 1, 384–400. 10.1016/S0022-328X(00)80030-3. - DOI
    3. Joy F.; Lappert M. F.; Prokai B. Chloroboration and Allied Reactions of Unsaturated Compounds: V. Haloboration and Phenyl-boration of Olefins; and the Preparation of Hexaphenyl-1,4-Diboracyclohexa-2,5-Diene. J. Organomet. Chem. 1966, 5, 506–519. 10.1016/S0022-328X(00)85153-0. - DOI

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