PMID- 37470697
OWN - NLM
STAT- PubMed-not-MEDLINE
LR  - 20230906
IS  - 1521-3773 (Electronic)
IS  - 1433-7851 (Linking)
VI  - 62
IP  - 37
DP  - 2023 Sep 11
TI  - Nickel-Catalyzed Selective C(sp(2) )-F Bond Alkylation of Industrially Relevant 
      Hydrofluoroolefin HFO-1234yf.
PG  - e202308690
LID - 10.1002/anie.202308690 [doi]
AB  - The selective transition-metal catalyzed C-F bond functionalization of 
      inexpensive industrial fluorochemicals represents one of the most attractive 
      approaches to valuable fluorinated compounds. However, the selective C(sp(2) )-F 
      bond carbofunctionalization of refrigerant hydrofluoroolefins (HFOs) remains 
      challenging. Here, we report a nickel-catalyzed selective C(sp(2) )-F bond 
      alkylation of HFO-1234yf with alkylzinc reagents. The resulting 
      2-trifluoromethylalkenes can serve as a versatile synthon for diversified 
      transformations, including the anti-Markovnikov type hydroalkylation and the 
      synthesis of bioactive molecule analogues. Mechanistic studies reveal that 
      lithium salt is essential to promote the oxidative addition of Ni(0) (L(n) ) to 
      the C-F bond; the less electron-rich N-based ligands, such as bipyridine and 
      pyridine-oxazoline, feature comparable or even higher oxidative addition rates 
      than the electron-rich phosphine ligands; the strong sigma-donating phosphine 
      ligands, such as PMe(3) , are detrimental to transmetallation, but the less 
      electron-rich and bulky N-based ligands, such as pyridine-oxazoline, facilitate 
      transmetallation and reductive elimination to form the final product.
CI  - (c) 2023 Wiley-VCH GmbH.
FAU - Luo, Yun-Cheng
AU  - Luo YC
AD  - Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic 
      Chemistry, University of Chinese Academy of Sciences, Chinese Academy of 
      Sciences, 345 Lingling Lu, Shanghai, 200032, China.
FAU - Wang, Ming-Kuan
AU  - Wang MK
AD  - Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic 
      Chemistry, University of Chinese Academy of Sciences, Chinese Academy of 
      Sciences, 345 Lingling Lu, Shanghai, 200032, China.
FAU - Yu, Ling-Chao
AU  - Yu LC
AD  - Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic 
      Chemistry, University of Chinese Academy of Sciences, Chinese Academy of 
      Sciences, 345 Lingling Lu, Shanghai, 200032, China.
FAU - Zhang, Xingang
AU  - Zhang X
AUID- ORCID: 0000-0002-4406-6533
AD  - Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic 
      Chemistry, University of Chinese Academy of Sciences, Chinese Academy of 
      Sciences, 345 Lingling Lu, Shanghai, 200032, China.
AD  - School of Chemistry and Material Sciences, Hangzhou Institute for Advanced Study, 
      University of Chinese Academy of Sciences, 1 Sub-lane Xiangshan, Hangzhou, 
      310024, China.
LA  - eng
GR  - 2021YFF0701700/National Key R&D Program of China/
GR  - 21931013/National Natural Science Foundation of China/
GR  - 21991122/National Natural Science Foundation of China/
GR  - 22JC1403500/the Science and Technology Committee of Shanghai Municipality/
GR  - 21XD1404400/Science and Technology Committee of Shanghai Municipality/
PT  - Journal Article
DEP - 20230801
PL  - Germany
TA  - Angew Chem Int Ed Engl
JT  - Angewandte Chemie (International ed. in English)
JID - 0370543
SB  - IM
OTO - NOTNLM
OT  - Alkylation
OT  - Cross-Coupling
OT  - C-F Bond Activation
OT  - HFO-1234yf
OT  - Nickel Catalysis
EDAT- 2023/07/20 13:06
MHDA- 2023/07/20 13:07
CRDT- 2023/07/20 09:44
PHST- 2023/06/20 00:00 [received]
PHST- 2023/07/20 13:07 [medline]
PHST- 2023/07/20 13:06 [pubmed]
PHST- 2023/07/20 09:44 [entrez]
AID - 10.1002/anie.202308690 [doi]
PST - ppublish
SO  - Angew Chem Int Ed Engl. 2023 Sep 11;62(37):e202308690. doi: 
      10.1002/anie.202308690. Epub 2023 Aug 1.