4.1. BoccTaHoeneHMe rMAPMAaMM 6opa
1.3. L.\11taH6opr11tAPMA HaTpMR (NaBH3CN) - p.cn. 3ae111c111r or pH
• npM pH<3 H/lM B npHCYTCTBMH KMC/lOT /lbtOMCa p.cn. cyw,ecreeHHO 803pacTaeT - BOCCTaHaB/lMBaeT Kap60HM/lbHble rpynnbl, OKCHMbl, T03H/lrHApa30Hbl, 3nOKCMAbl, reTepOL\MK/lbl.
OH
OH
THF
OH
MeOH/HCI
AcOH
Me
AcOH/TFA/T
DMF/
CYJlb(pOJlaH
4.1. BoccTaHOBneHMe rMAPMAaMM 6opa
1.4. TpHaL\eTOKCM6oprMAPMA HarpHH (NaBH(OAch} 'in situ' NaBH4 /3AcOH
e MeHee aKTMBeH 'teM NaBH4, ce/leKTMBHO BOCCTaHaBnMeaeT anbAerMAbl.
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npMMeHRtoT AJIR BOCCTaHOBMTe/lbHOro aMMHMpoeaHMR (MeTOA 6opxa) |
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0 |
OH |
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H |
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NaBH(OAch |
• CKOPOCTb BOCCTaHOBneHMff B03pacTaeT npM HanM'tMM B 13-nono>t<eHMM rMAPOKCMrpynnbl. peaKU.Mff npoTeKaeT CTepeoce11eKTMBHO K3K aHTM-npMCOeAMHeHMe rMAPMA-MOHa
H |
OAc |
b |
NaB ( |
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-----►._ |
AcOH |
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OTB DPS |
OH |
NaBH(OAc)3 |
.. |
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► |
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MeCN/AcOH |
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O |
OAc |
; |
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f |
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R |
-gt.o--s.......... |
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1 |
11111111 |
/ OAc |
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H |
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R2 |
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OH |
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OTB DPS |
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0 |
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0 |
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,,)l_OMe |
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NaBH(OAcb |
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-----►.. |
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- |
AcOH |
4.1. BoccraHoeneHMe rHAPMAaMM 6opa
1.4. Tp1-1a4eroKcM6oprMAPHA HaTpHff (NaBH(OAc)3) 'in situ' NaBH4 /3AcOH
• HaM6011ee 34>4>eKTMBHblM peareHT AJUI BOCCTaHOBMTe/lbHOro aMMHMpoeaHMSI Kap60HM/lbHblMM COeAMHeHMSIMM, a 8 >KeCTKMX ycnOBMSIX Kap60HOBblMM KMCnOT3MM
NH2
o==<:::l-'<O E
NaBH(OAch
DCE
Na8H4
NH2 ------11►►
EtC02H/.6.
OMe
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I\ |
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0 |
HN |
NBoc |
'>--1< |
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\_J |
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N OMe |
NaBH(o:C)J |
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_) |
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OCE |
BocN |
NH2Bn
------•
NaBH(OAcb
DCE
4.1. BoccTaHOBneHMe rMAPMA3MM 6opa
1.5. CeneKTPMAbl |
LiAIH(OMeh |
s-Bu |
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◄ |
s, |
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s-Bu s-Bu |
• CTepM'4eCKM 3aTPYAHeHHble KeTOHbl BOCCTaHOBMTe/lM C BblCOKOH perMO- M CTepeoceneKTMBHOCTbtO. "1cno11b3YtOT AJlff BOCCTaHOB/leHMff KeTOHOB
_..-··--.- e---
OH L-cenElKTpHA
..______.--r--H
---.t. -...6 (e-)
97%
-
NaBH |
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------4►.. |
{_ u |
CeCl3 |
(a |
H |
3n111ranaHTaMIIIH |
-) |
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4.1. BoccTaHoeneHMe rMAPMAaMM 6opa
1.5. CeneKTPMAbl
OH L-ceneKTp .QH OH
|
OH |
OH |
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PGE2 (.Q111HonpocroH) |
|
PGF2 (,D.111Honpocr) |
• BoccTaHOB/leHHe a,'3-HenpeAe/lbHblX KeTOHOB-
O 1.L-ceneKTp .Q/THF |
0 |
|
► |
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KapBOMeHTOH |
ttO |
L-ceneKTp .Q |
H |
• BoccTaHOB/leHHe/a11KH/1HpoeaHHe |
6 |
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►
THF
a,'3-HenpeAe/lbHblX KeT HOB
©
Oli------ |
|
- ( f ) |
I |
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Br |
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H p |
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4.1. BoccraHoeneHHe rHAPHAaMH 6opa
2. 6opaHbl |
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2.1. 6opaH (BH3)2 |
(<<in situ>> Na BH4/BF3* Et2O), |
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KOMn/leKCbl : |
BH3 |
* THF; BH3 |
* SMe2 (BMS) |
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• rMAp060pMpOBaHMe H BOCCTaHOB/leHMe a/lKeHOB, anKMHOB |
..R |
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Nao:, R |
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\ |
-- b [ \--: |
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] |
* |
.. R |
H20'. \_::\e -o"H |
* |
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H |
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H--BH |
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BH |
NaOH . |
H B |
/ |
] |
0 |
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O-a/ |
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OH |
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[ |
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-O |
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R (HCO?.. i O J O |
'' |
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\_ |
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I |
R H |
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R1---R2 |
► |
R |
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2 |
2 |
;.. |
[ |
R)=( |
2 |
] |
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- |
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R |
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O |
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)== |
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6- 6+ |
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( |
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. |
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H-BH2 |
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H 0 |
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►.. |
Y |
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H |
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BH2 |
NaOH |
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H OH |
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2 |
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R2 |
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(±) |
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( |
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H!) |
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H |
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R |
= |
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(HC02H)
4.1. BoccraHoeneHMe rMAPHAaMM 6opa
2.1. 6opaH (BH3 )i
• MOW,HblM BOCCTaHOBMTenb <l>YHKL\MOH3/lbHblX rpynn |
R-{ |
>> |
|
R-f |
> >=< |
> |
R-{ |
> M > |
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PRA peaK'-'MOHHOM cnoco6HocTM <l>YHK'-'MM: |
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0 |
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0 |
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0 |
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OH |
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R' |
0 |
N- |
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0 |
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'}-o |
.,,,OH 1. |
|
OH |
EtO |
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BH3/THF |
HO |
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► |
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OH 1.SOCl2 |
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EtO |
0 |
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NPr2 //\. |
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\_j/ |
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► |
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0 |
OEt |
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NaOEt► |
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2. HNPr2 |
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NaOH |
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Pd/C |
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HN |
PonMHHpon |
OEt |
HO |
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0 |
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4.1. BoccraHoeneHHe rHAPHAaMH 6opa
2.1. 6opaH (BH3)2
HE!AOCTaTKH:
•6opaH npM fMAP06opMpoeaHMM anK@HOB npMBOAHT K CM@CM MOHO-, AM- M TpManKMn6opaHOB,
•rMAP06opMpoeaHMM anKMHOB Moryr o6pa30Bb1B3TbCff anKMnAM6opaHbl
• HM3KOM 4YBCTBMTenbHOCTbto K crepM4eCKMM npenffTCTBMffM
BH2
2.2. AnKMn6opaHbl HB(Sia)2, H2BThx, 9-BBN
|
|
BH3 |
B |
|
F THF► |
|
H |
|
>=< |
THF... |
HB(Sia)2 |
|
>-t2 |
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BH3 |
|
H2 BThx
43% +Y'(
57%
|
H |
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I |
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B |
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BH3 |
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- H-B |
THF |
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► |
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9-BBN |
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4.1. BoccraHoeneHMe rHAPHAaMH 6opa
2.2. A11KM116opaHbl HB(Sia)z, H2 8Thx, 9-BBN
• Mcnonb3VIOT Anff pen oceneKTMBHOro rMAP060pMpoeaHMff anKeHOB M anKMHOB:
0
9-BBN
• AManKMn6opaHbl 6onee cna6b1e BOCCTaHOBMTenM "leM 6opaH - MX
MCnOnb3VIOT AJlff perMOCe/leKTMBHOroBOCCTaHOB/leHMff Kap60HMnbHblX rpynn |
6 |
|
.. |
97°/o |
0 |
....... He |
H |
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O H |
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Ph |
HaSia |
a-.., |
Ph |
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._, |
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THF |
• AManKMn6opaHbl He BOCCTaHaB/IMBalOT KMCnOTbl M 1° aMMAbl, |
HO BOCCTaHaB/1"1B3IOT |
3° aMMAbl AO anbAerMAOB |
P _/Jo |
HBSia► |
P -{. |
|
h\ |
2 |
h |
OH |
THF |
|
H |
NMe2 |
|
|
NMe2 |
4.1. BoccraHoeneHHe rHAPHAaMM 6opa
2.3. ACCMMeTpMl.4eCKHe 6opaHbl: lpc2BH, anbnMH6opaH, CBS-OKCa3a6opo11HAHH
• lpc2BH Mcnonb3YtOT Anst cTepeoceneKTMBHoro rMAP06opMpoeaHMst
|
H |
F\ |
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|
,,,, B |
|
THF |
;@ |
0 |
a-n"1H9H |
lpc2BH |
|
|
I |
|
|
Bz |
• Al1bnMH6opaHbl (R,S-) Mcnonb3VIOT AJ1SI CTepeoceneKTMBHOro BOCCTaHOBneHMSI KeTOHOB (eocCTaHoeneHMe no MMAJ1eHAY)
(R)-anbn H- |
► HXOH |
6opaH► |
