PMID- 29603551
OWN - NLM
STAT- PubMed-not-MEDLINE
LR  - 20191120
IS  - 1521-3773 (Electronic)
IS  - 1433-7851 (Linking)
VI  - 57
IP  - 22
DP  - 2018 May 28
TI  - Expanding the Chemistry of the Class C Radical SAM Methyltransferase NosN by 
      Using an Allyl Analogue of SAM.
PG  - 6601-6604
LID - 10.1002/anie.201712224 [doi]
AB  - The radical S-adenosylmethionine (SAM) superfamily enzymes cleave SAM reductively 
      to generate a highly reactive 5'-deoxyadenosyl (dAdo) radical, which initiates 
      remarkably diverse reactions. Unlike most radical SAM enzymes, the class C 
      radical SAM methyltransferase NosN binds two SAMs in the active site, using one 
      SAM to produce a dAdo radical and the second as a methyl donor. Here, we report a 
      mechanistic investigation of NosN in which an allyl analogue of SAM (allyl-SAM) 
      was used. We show that NosN cleaves allyl-SAM efficiently and the resulting dAdo 
      radical can be captured by the olefin moieties of allyl-SAM or 
      5'-allylthioadenosine (ATA), the latter being a derivative of allyl-SAM. 
      Remarkably, we found that NosN produced two distinct sets of products in the 
      presence and absence of the methyl acceptor substrate, thus suggesting 
      substrate-triggered production of ATA from allyl-SAM. We also show that NosN 
      produces S-adenosylhomocysteine from 5'-thioadenosine and homoserine lactone. 
      These results support the idea that 5'-methylthioadenosine is the direct methyl 
      donor in NosN reactions, and demonstrate great potential to modulate radical SAM 
      enzymes for novel catalytic activities.
CI  - (c) 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
FAU - Ji, Xinjian
AU  - Ji X
AD  - Department of Chemistry, Fudan University, Shanghai, 200433, China.
FAU - Mandalapu, Dhanaraju
AU  - Mandalapu D
AD  - Department of Chemistry, Fudan University, Shanghai, 200433, China.
FAU - Cheng, Jinduo
AU  - Cheng J
AD  - Department of Chemistry, Fudan University, Shanghai, 200433, China.
FAU - Ding, Wei
AU  - Ding W
AD  - Department of Chemistry, Fudan University, Shanghai, 200433, China.
FAU - Zhang, Qi
AU  - Zhang Q
AUID- ORCID: 0000-0002-8135-2221
AD  - Department of Chemistry, Fudan University, Shanghai, 200433, China.
LA  - eng
PT  - Journal Article
PT  - Research Support, Non-U.S. Gov't
DEP - 20180426
PL  - Germany
TA  - Angew Chem Int Ed Engl
JT  - Angewandte Chemie (International ed. in English)
JID - 0370543
OTO - NOTNLM
OT  - S-adenosylmethionine
OT  - biosynthesis
OT  - radical SAM enzymes
OT  - radical reactions
OT  - sulfonium radical
EDAT- 2018/04/01 06:00
MHDA- 2018/04/01 06:01
CRDT- 2018/04/01 06:00
PHST- 2017/11/28 00:00 [received]
PHST- 2018/02/11 00:00 [revised]
PHST- 2018/04/01 06:00 [pubmed]
PHST- 2018/04/01 06:01 [medline]
PHST- 2018/04/01 06:00 [entrez]
AID - 10.1002/anie.201712224 [doi]
PST - ppublish
SO  - Angew Chem Int Ed Engl. 2018 May 28;57(22):6601-6604. doi: 
      10.1002/anie.201712224. Epub 2018 Apr 26.