Scalable Synthesis of Highly Reactive 1,3-Diaminodienes from Vinamidinium Salts and Their Use in Diels-Alder Reactions Sida Zhou, Eduardo Sánchez-Larios, and Michel Gravel*
[email protected] Department of Chemistry, University of Saskatchewan 110 Science Place, Saskatoon, SK, S7N 5C9, Canada
Supporting Information Table of Contents Copies of NMR Spectra ..................................................................................................................................................... 2 (3E)‐4‐morpholinyl‐3‐buten‐2‐one (11a) .......................................................................................................... 2 (Z)‐1‐(3‐methoxybut‐2‐enylidene)morpholinium tetrafluoroborate (12a) ........................................ 3 (Z)‐1‐(3‐methoxybut‐2‐enylidene)piperidinium tetrafluoroborate (12b)........................................... 4 (Z)‐1‐(3‐methoxybut‐2‐enylidene)pyrrolidinium tetrafluoroborate (12c) ......................................... 5 (Z)‐1‐(3‐(morpholinyl)but‐2‐enylidene)morpholinium tetrafluoroborate (4a)................................ 6 (Z)‐1‐(3‐(piperidinyl)but‐2‐enylidene)piperidinium tetrafluoroborate (4b)..................................... 7 (Z)‐1‐(3‐(pyrrolidinyl)but‐2‐enylidene)pyrrolidinium tetrafluoroborate (4c).................................. 8 4‐(pyrrolidin‐1‐yl)cyclohexa‐1,3‐dienecarbaldehyde (21) ......................................................................... 9 Methyl 1‐methyl‐4‐oxocyclohex‐2‐enecarboxylate (22) ............................................................................10 Methyl 6‐phenyl‐4‐(pyrrolidin‐1‐yl)cyclohexa‐1,3‐dienecarboxylate (23)........................................11 N,N‐diethyl‐4‐(phenylamino)‐5‐(pyrrolidin‐1‐yl)biphenyl‐2‐carboxamide (27)............................12 Competition Experiment Between Rawal’s Diene (28) and Diaminodiene 5c ..................................13
S1
Copies of NMR Spectra (3E)-4-morpholinyl-3-buten-2-one (11a)
S2
(Z)-1-(3-methoxybut-2-enylidene)morpholinium tetrafluoroborate (12a)
S3
(Z)-1-(3-methoxybut-2-enylidene)piperidinium tetrafluoroborate (12b)
O
BF4
N
S4
(Z)-1-(3-methoxybut-2-enylidene)pyrrolidinium tetrafluoroborate (12c)
O
BF4
S5
N
(Z)-1-(3-(morpholinyl)but-2-enylidene)morpholinium tetrafluoroborate (4a)
O N
BF4
N O
S6
(Z)-1-(3-(piperidinyl)but-2-enylidene)piperidinium tetrafluoroborate (4b)
N
BF4
N
S7
(Z)-1-(3-(pyrrolidinyl)but-2-enylidene)pyrrolidinium tetrafluoroborate (4c)
N
BF4
S8
N
4-(pyrrolidin-1-yl)cyclohexa-1,3-dienecarbaldehyde (21)
S9
Methyl 1-methyl-4-oxocyclohex-2-enecarboxylate (22)
O OMe O
S10
Methyl 6-phenyl-4-(pyrrolidin-1-yl)cyclohexa-1,3-dienecarboxylate (23)
S11
N,N-diethyl-4-(phenylamino)-5-(pyrrolidin-1-yl)biphenyl-2-carboxamide (27)
N
H N
Ph
Ph O
N
S12
Competition Experiment Between Rawal’s Diene (28) and Diaminodiene 5c O
H1
H2
CH3
1
H
H2
H3
H3
N H2
H1
H2
H1
TBSO
H1
N H2
O
H2
H1
TBSO
H 1
H2
Competition experiment 13c N 1
H
N
O
H1
H1
H2
S13
