PMID- 35226811
OWN - NLM
STAT- MEDLINE
DCOM- 20220421
LR  - 20220421
IS  - 1520-5126 (Electronic)
IS  - 0002-7863 (Linking)
VI  - 144
IP  - 9
DP  - 2022 Mar 9
TI  - Mechanistic Details of Asymmetric Bromocyclization with BINAP Monoxide: 
      Identification of Chiral Proton-Bridged Bisphosphine Oxide Complex and Its 
      Application to Parallel Kinetic Resolution.
PG  - 3913-3924
LID - 10.1021/jacs.1c11816 [doi]
AB  - The mechanism of our previously reported catalytic asymmetric bromocyclization 
      reactions using 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP) monoxide was 
      examined in detail by the means of control experiments, NMR studies, X-ray 
      structure analysis, and CryoSpray electrospray ionization mass spectrometry 
      (ESI-MS) analysis. The chiral BINAP monoxide was transformed to a key catalyst 
      precursor, proton-bridged bisphosphine oxide complex (POHOP.Br), in the presence 
      of N-bromosuccinimide (NBS) and contaminating water. The thus-formed POHOP 
      further reacts with NBS to afford BINAP dioxide and molecular bromine (Br(2)) 
      simultaneously in equimolar amounts. While the resulting Br(2) is activated by 
      NBS to form a more reactive brominating reagent (Br(2) horizontal line NBS), BINAP dioxide serves 
      as a bifunctional catalyst, acting as both a Lewis base that reacts with 
      Br(2) horizontal line NBS to form a chiral brominating agent (P horizontal lineO(+) horizontal line Br) and also as a Bronsted 
      base for the activation of the substrate. By taking advantage of this novel 
      concerted Lewis/Bronsted base catalysis by BINAP dioxide, we achieved the first 
      regio- and chemodivergent parallel kinetic resolutions (PKRs) of racemic 
      unsymmetrical bisallylic amides via bromocyclization.
FAU - Yamashita, Kenji
AU  - Yamashita K
AUID- ORCID: 0000-0003-1747-1493
AD  - School of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Suruga-ku, 
      Shizuoka 422-8526, Japan.
FAU - Hirokawa, Ryo
AU  - Hirokawa R
AD  - School of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Suruga-ku, 
      Shizuoka 422-8526, Japan.
FAU - Ichikawa, Mamoru
AU  - Ichikawa M
AD  - School of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Suruga-ku, 
      Shizuoka 422-8526, Japan.
FAU - Hisanaga, Tatsunari
AU  - Hisanaga T
AD  - School of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Suruga-ku, 
      Shizuoka 422-8526, Japan.
FAU - Nagao, Yoshihiro
AU  - Nagao Y
AD  - School of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Suruga-ku, 
      Shizuoka 422-8526, Japan.
FAU - Takita, Ryo
AU  - Takita R
AUID- ORCID: 0000-0003-4104-9890
AD  - Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, 
      Bunkyo-ku, Tokyo 113-0033, Japan.
FAU - Watanabe, Kohei
AU  - Watanabe K
AUID- ORCID: 0000-0002-3146-5439
AD  - Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, 
      Bunkyo-ku, Tokyo 113-0033, Japan.
FAU - Kawato, Yuji
AU  - Kawato Y
AD  - School of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Suruga-ku, 
      Shizuoka 422-8526, Japan.
FAU - Hamashima, Yoshitaka
AU  - Hamashima Y
AUID- ORCID: 0000-0002-6509-8956
AD  - School of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Suruga-ku, 
      Shizuoka 422-8526, Japan.
LA  - eng
PT  - Journal Article
PT  - Research Support, Non-U.S. Gov't
DEP - 20220228
PL  - United States
TA  - J Am Chem Soc
JT  - Journal of the American Chemical Society
JID - 7503056
RN  - 0 (BINAP, 2-naphthol)
RN  - 0 (Naphthalenes)
RN  - 0 (Oxides)
RN  - 0 (Protons)
SB  - IM
MH  - Catalysis
MH  - Naphthalenes/chemistry
MH  - *Oxides
MH  - *Protons
EDAT- 2022/03/01 06:00
MHDA- 2022/04/22 06:00
CRDT- 2022/02/28 20:03
PHST- 2022/03/01 06:00 [pubmed]
PHST- 2022/04/22 06:00 [medline]
PHST- 2022/02/28 20:03 [entrez]
AID - 10.1021/jacs.1c11816 [doi]
PST - ppublish
SO  - J Am Chem Soc. 2022 Mar 9;144(9):3913-3924. doi: 10.1021/jacs.1c11816. Epub 2022 
      Feb 28.