PMID- 30408240
OWN - NLM
STAT- PubMed-not-MEDLINE
DCOM- 20190130
LR  - 20190130
IS  - 1521-3765 (Electronic)
IS  - 0947-6539 (Linking)
VI  - 25
IP  - 6
DP  - 2019 Jan 28
TI  - Stable and Persistent Acyclic Diaminocarbenes with Cycloalkyl Substituents and 
      Their Transformation to beta-Lactams by Uncatalysed Carbonylation with CO.
PG  - 1488-1497
LID - 10.1002/chem.201805307 [doi]
AB  - Four new acyclic diaminocarbenes (ADACs), viz. [(cyclo-C(n) H(2n-1) )(2) N](2) C 
      (n=5-7) and iPr(2) N-C-N(cyclo-C(6) H(11) )(2) , were synthesised by reacting the 
      corresponding formamidinium hexafluorophosphates with NaN(SiMe(3) )(2) . Their 
      nucleophilicities and electrophilicities were respectively judged from the (1) 
      J(CH) values determined for the N(2) CH unit of the corresponding formamidinium 
      cations and from the (77) Se NMR chemical shifts of the selenourea derivatives 
      obtained from the reaction of elemental selenium with the corresponding ADACs. An 
      ambiphilic profile essentially identical to that of the "Alder carbene" (iPr(2) 
      N)(2) C was found in each case. Similar to the latter carbene, the new ADACs 
      undergo a well-defined thermal decomposition by beta-fragmentation, affording an 
      alkene and a formamidine. The stabilities of [(cyclo-C(n) H(2n-1) )(2) N](2) C 
      depend strongly on the value of n, following the order 6>5>7, with the latter 
      congener being too unstable for isolation. [(cyclo-C(6) H(11) )(2) N](2) C shows 
      no thermal decomposition at room temperature in solution and is thus 
      significantly more stable than (iPr(2) N)(2) C. The stability of iPr(2) 
      N-C-N(cyclo-C(6) H(11) )(2) is intermediate between that of (iPr(2) N)(2) C and 
      [(cyclo-C(6) H(11) )(2) N](2) C, its beta-fragmentation selectively affording 
      propene and iPrN=CH-N(cyclo-C(6) H(11) )(2) . [(cyclo-C(n) H(2n-1) )(2) N](2) C 
      (n=5-7) react readily with CO under mild conditions, selectively affording 
      trisubstituted spirocyclic beta-lactam derivatives with an antimicrobial activity 
      spectrum similar to that of penicillin G.
CI  - (c) 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
FAU - Wallbaum, Lars
AU  - Wallbaum L
AD  - Institute of Chemistry, University of Kassel, Heinrich-Plett-Strasse 40, 34132, 
      Kassel, Germany.
FAU - Weismann, Daniel
AU  - Weismann D
AD  - Institute of Chemistry, University of Kassel, Heinrich-Plett-Strasse 40, 34132, 
      Kassel, Germany.
FAU - Lober, Dennis
AU  - Lober D
AD  - Institute of Chemistry, University of Kassel, Heinrich-Plett-Strasse 40, 34132, 
      Kassel, Germany.
FAU - Bruhn, Clemens
AU  - Bruhn C
AD  - Institute of Chemistry, University of Kassel, Heinrich-Plett-Strasse 40, 34132, 
      Kassel, Germany.
FAU - Prochnow, Pascal
AU  - Prochnow P
AD  - Biology of Microorganisms, Ruhr University Bochum, Universitatsstrasse 150, 44801, 
      Bochum, Germany.
FAU - Bandow, Julia E
AU  - Bandow JE
AD  - Biology of Microorganisms, Ruhr University Bochum, Universitatsstrasse 150, 44801, 
      Bochum, Germany.
FAU - Siemeling, Ulrich
AU  - Siemeling U
AUID- ORCID: 0000-0002-8617-7768
AD  - Institute of Chemistry, University of Kassel, Heinrich-Plett-Strasse 40, 34132, 
      Kassel, Germany.
LA  - eng
GR  - SI 429/19-1 and 429/19-2/Deutsche Forschungsgemeinschaft/
PT  - Journal Article
DEP - 20181227
PL  - Germany
TA  - Chemistry
JT  - Chemistry (Weinheim an der Bergstrasse, Germany)
JID - 9513783
OTO - NOTNLM
OT  - amines
OT  - carbenes
OT  - carbonylation
OT  - lactams
OT  - selenourea derivatives
EDAT- 2018/11/09 06:00
MHDA- 2018/11/09 06:01
CRDT- 2018/11/09 06:00
PHST- 2018/10/23 00:00 [received]
PHST- 2018/11/07 00:00 [revised]
PHST- 2018/11/09 06:00 [pubmed]
PHST- 2018/11/09 06:01 [medline]
PHST- 2018/11/09 06:00 [entrez]
AID - 10.1002/chem.201805307 [doi]
PST - ppublish
SO  - Chemistry. 2019 Jan 28;25(6):1488-1497. doi: 10.1002/chem.201805307. Epub 2018 
      Dec 27.