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. 2024 Nov 19;15(47):20064-20072.
doi: 10.1039/d4sc07036d. eCollection 2024 Dec 4.

Ru(ii)-catalyzed regioselective oxidative Heck reaction with internal olefins that tolerated strongly coordinating heterocycles

Ci Chen  1 , Qiaoya Zhang  1 , Zhiwei Huang  1 , Wensen Ouyang  1 , Yang Gao  1 , Jiye Luo  1 , Yuan Liu  1 , Yanping Huo  1 , Qian Chen  1 , Xianwei Li  1
Affiliations

Ru(ii)-catalyzed regioselective oxidative Heck reaction with internal olefins that tolerated strongly coordinating heterocycles

Ci Chen et al. Chem Sci. .

Abstract

The oxidative Heck reaction of strongly coordinating heterocycles with internal olefins often led to elusive reactivity and regioselectivity. Herein, by judicious choice of X-type directing groups under Ru(ii) catalysis, we achieved the regioselective oxidative Heck reaction of strongly coordinating heterocycles with sterically demanding internal olefins. It was postulated that the "match/mismatch effect" of sterically demanding internal olefins as coupling partners and subsequent kinetically favoured Michael addition or oxidative aromatization act as driving forces to facilitate the desired reactivity and site-selectivity.

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Conflict of interest statement

There are no conflicts to declare.

Figures

Scheme 1
Scheme 1. Regioselective oxidative Heck reaction with internal olefins that tolerated strongly coordinating heterocycles.
Scheme 2
Scheme 2. Regioselective oxidative Heck reaction of heterocycles with internal olefins.
Scheme 3
Scheme 3. Preliminary mechanistic studies.
Scheme 4
Scheme 4. Regioselective oxidative Heck reaction with internal olefins.
Scheme 5
Scheme 5. N–OPiv oxime enabled oxidative Heck reaction of heterocycles with sterically demanding internal olefins.
Scheme 6
Scheme 6. Mechanistic studies.
Scheme 7
Scheme 7. Synthetic transformations. Conditions: (a) 3b (0.1 mmol), NaOAc (2.0 equiv.), NH2OH·HCl (2.0 equiv.), MeOH/H2O (1.0 mL/1.0 mL), 90 °C, 2 h; (b) 3b (0.1 mmol), NaN3 (4.0 equiv.), NH4Cl (2.0 equiv.), DMF (1.0 mL), N2, 120 °C, 24 h; (c) 3b (0.1 mmol), NaOH aqueous solution (3 equiv., 3 M), 80 °C, 15 h; (d) 3b-V (0.05 mmol), K2CO3 (2.0 equiv.), MeI (2.0 equiv.), THF (1.0 mL), 40 °C, 5 h; (e) 3e (0.10 mmol), Pd(PPh3)4 (0.005 mmol), K2CO3 (0.4 mmol), Ar–B(OH)2 (0.12 mmol), EtOH/H2O/toluene = (0.3 mL/0.4 mL/1.0 mL), 95 °C, 12 h.
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