Scalable Synthesis of Highly Reactive 1,3-Diamino ... - ACS Publications

Sida Zhou, Eduardo Sánchez-Larios, and Michel Gravel*. Department of Chemistry, University of Saskatchewan, 110 Science Place, Saskatoon SK S7N 5C9, ...
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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