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Synthèse de machines moléculaires pour le contrôle de mouvements de rotation et de translation

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(67) &,*'-,!'& G: %',-*-&!!*,!'&&$*!& . ,1 *# "-+',# "# * !&'+'# "#1 +!&',#1 +-*>!3*'0#1Q *Z>/3'.# "# #0',% . $-02#+#,2 .02'!'.> 3 ">4#*-..#+#,2 "#1 +-2#301 +-*>!3*'0#1 3,'"'0#!2'-,,#*1 *'+#,2>1 .0 3, 12'+3*31 *3+',#36T .0=1 *# ">4#*-..#+#,2 "# "#36 +-2#301 3,'"'0#!2'-,,#*1 "# .0#+'=0#wv #2 "#36'=+# %>,>02'-,wwQ #0',% #2 !-**T 0#,"#,2 !-+.2# #, wuvv "# * 17,2&=1# #2 "3 $-,!2'-,,#+#,2 "Z3, ,-34#3 +-2#30 1> *3' 311' 130 *# $0%+#,2 2&'-6,2&=,#wx `'%30# ~aT # +-2#30 3,'"'0#!2'-,,#*  * .02'!3*0'2>"#.-34-'0!&,%#0"#1#,1"#0-22'-,13'4,23,.0-!#1131!-,20D*>T S. Me2NOC. S. Me. S.    . !-*Z>(*6+&,,!'&++,*-,-*+. .   . S.   . . !%!)-++%',-*+*!&R5*<S5%,T5%6&6*,!'&+?. #+-2#30"#.0#+'=0#%>,>02'-,`Da#12 1>1303,*!=,#&>*'!-B"*!&'0*T.  0-22'-, 3,'"'0#!2'-,,#**# 32-30 "# * *''1-, ƒ !#,20*# #12 ',"3'2# .0 /320# >2.#1 2&#0+'/3#+#,2 -3 .&-2-!&'+'/3#+#,2 !2'4>#1T ,1 !# !1 "# $'%30#Q *# +-34#+#,2 3,'"'0#!2'-,,#* #12 .-11' *# %0:!# 9 * !&'0*'2> "3 1712=+# ',1' /3Z9 *Z..-02"Z>,#0%'#*3+',#31#T0'**#301Q3!3,#"'$$>0#,!'2'-,#,20#*.02'#0-2-0#2 * .02'# 122-0 ,# .#32 ?20# $'2#Q .3'1/3# *#1 "#36 .02'#1 "# * +-*>!3*# 1-,2 '"#,2'/3#1T . # ">4#*-..#+#,2 "Z3, +-2#30 "# 1#!-,"# %>,>02'-, `Ea ..-02# /3#*/3#1. +>*'-02'-,1 9 1-, $-,!2'-,,#+#,2T  0-22'-, "3 +-2#30 E #12 .*31 0.'"# /3# .0>!>"#++#,2Q * .02'# 122-0 .#32 ?20# +',2#,,2 "'$$>0#,!'># "# * .02'# 0-2-0 #2 *Z',20-"3!2'-,"#1%0-3.#+#,211-3$0>1"-,,#*.-11' '*'2>"#*'#0*#+-2#309"Z320#1 +-*>!3*#1 -3 >4#,23#**#+#,2 9 3,# 130$!# +>2**'/3#T Z3,'"'0#!2'-,,*'2> "3 +-2#30 #12 +',2#,,2 1130># *-01 "# *Z>2.# "Z',4#01'-, "# *Z&>*'!'2> `.11%# "Z3, !7!*# .&>,7*# "30-2-03V"#*9"3122-09*+,'=0#"Z3,#0-3#90-!&#2#2!*'/3#2aT #1#,1 "# * 0-22'-, #12 /3,2 9 *3' !-,20D*> .0 *# !#,20# 12>0>-%>,'/3# .-02,2 '!' 3, %0-3.#+#,2+>2&7*#T . *-01/3#*#1"#36.0#+'#01+-2#301!-,"3'1#,293,#0-22'-,3,'"'0#!2'-,,#**#Q. *#+-2#30"#20-'1'=+#%>,>02'-,`Fa>2>">4#*-..>",1*# 32"#.-34-'0',4#01#0 . RX.

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xZ3 *'#3"#wZ.00..-029*"-3 *#*''1-,#12,>!#11'0#$',"Z>4'2#0*12 '*'12'-,"#* .-1'2'-, **7*'/3# *-01 "# * ">.0-2-,2'-,T #22# 12 '*'12'-, 0#,"0'2 *Z>.'+>0'12'-, +-',1#$$'!!#.3'1/3#*#!0 ,'-,1#0'2+-',10>!2'$T Me2NOC. S. S. Me2NOC. hv. Base . hv. 

(69)    . S.

(70)  

(71)   (3'S)-(P)-1' Clockwise     rotation.  Step 4.  Step 2. S. S. CONMe2. S. Epimerization changes the direction of rotation. 

(72)    . S.

(73)  

(74)   (3'S)-(M)-1.

(75)  

(76)   (3'R)-(M)-1' Anticlockwise      rotation.   Step 2'.   Step 4'. S. Me2NOC. CONMe2. S. hv. Step 5'  . Step 3 . S. S.

(77)  

(78)   (3'R)-(P)-1.  Base. hv.

(79)  

(80)   (3'S)-(P)-1'. CONMe2.   Step 1'. S. S. S.  Step 5.

(81)  

(82)   (3'S)-(M)-1. Me2NOC. b. CONMe2.  Step 1. Step 3'   S.

(83)  

(84)   (3'R)-(M)-1'. S.

(85)  

(86)   (3'R)-(P)-1. . !-*RQ>(*6+&,,!'&+ 6%,!)-+1$+*',,!'& '*!*,&,! '*!*'&,*8$6+-%',-*F?. . # $-,!2'-,,#+#,2 "3 +-2#30 F #12 0#.0>1#,2> '%30# vuT Z'00"'2'-,. .&-2-!&'+'/3# "# *Z'1-+=0# `xZaV`aVF ',"3'2 3,# 0-22'-, "3 0-2-0 ",1 *# 1#,1 &-0'0# "-,,,2 *'#3 9 * $-0+2'-, "# *Z'1-+=0# `xZaV`aVF; +-',1 12 *#Q .3'1/3# *# %0-3.#+#,2 "'+>2&7*!0 +'"# 1# 20-34# #, .-1'2'-, .1#3"-6'*# .0 0..-02 3 122-0Q .-1'2'-, 12>0'/3#+#,2 ">$4-0 *# `>2.#vaT ,# ',4#01'-, "Z&>*'!'2> 2&#0+'/3#+#,2 !2'4># 20,1$-0+# *Z'1-+=0# `xZaV`aVF; #, `xZaV`aVF .*31 12 *#Q >2,2"-,,>/3#*#%0-3.#+#,2"'+>2&7*!0 +'"#0#4'#,2#,.-1'2'-,>/32-0'*#.0 0..-023122-0T#22#>2.#.#0+#230-2-0"#$0,!&'0*#!7!*# #,8>,'/3#"3122-0 9 * +,'=0# "Z3,# 0-3# 9 0-!&#2 #2 !*'/3#2 #2 $-0!# .0 !-,1>/3#,2 *# 1712=+# 9 1# ">.*!#0",13,#1#3*##2+?+#"'0#!2'-,`>2.#waT,#1#!-,"#'00"'2'-,',"3'23,# 0-22'-, ",1 *# 1#,1 &-0'0# #2 20,1$-0+# *Z'1-+=0# `xZaV`aVF #, '1-+=0#. RY .

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